CN1162005A - Lubricant oil - Google Patents

Abstract

The present invention is a process for preparing a lubricant oil with a viscosity index not lower than 120 DEG C and a pour point not higher than -45 DEG C. The process comprises the steps of (a) low-polyolefin feeding to form a lubricant oil, in the presence of a catalyst containing halogenated alkyl aluminum and alkylhalide; (b) separating the lubricant oil from the catalyst; and (c) selectively catalysis-hydrogenating the lubricant oil. The materials fed is a mixture containing at least 30% by weight (w/w) of C7-C91 olefin hydrocarbon, the mol ratio of the alkylhalide to the halogenated alkyl aluminium is within the range of 1.0:1-20, and the low polymerization is carried out at a temperature not higher than 50 DEG C.

Description

Lubricating oil

The present invention relates to by containing the method that the parallel feeding of heptene at least prepares lubricating oil.

Make the 1-olefin oligomerization become the hydrocarbon of higher molecular weight, it is known making the oligopolymer hydrogenation of formation or the method that isomerization generates lubricating oil (referring to, US-A-3763244 for example) then.As a rule, it is to obtain (by so-called " ethylene chain increases and displacement " method) by ethene that 1-alkene begins, and ethene is the expensive relatively raw material of this 1-alkene.In addition, lubricating oil makes (referring to US-A-3780128 and EP-A-0468109) by oligomeric pure relatively 1-alkene.This last piece document also discloses following content: once oligopolymer makes, the oligopolymer of various 1-alkene can mix the lubricating oil that has desired properties such as viscosity index and pour point with preparation before or after hydrogenation or isomerization steps.Similarly, US-A-4041098 has described the oligomeric 1-alkene of catalyzer that a kind of use contains alkyl aluminum halide and alkylogen such as tertiary butyl chloride to form the method for lubricating oil.Use conventional charging, for example commercially available 1-alkene such as 1-hexene or 1-decene can not produce the lubricating oil of required viscosity index.For example, basically the charging that contains pure alkene such as 1-decene has obtained having the lubricant of relative high viscosity index (HVI), but it is the unit of 10 multiple that these products only contain, because being desired decylene oligomer and its, this is containing 30,40, occupy an leading position in the individual elements of 50,60 and 70 carbon atoms.Though this mixture is suitable for some purposes, but it is not the ideal synthetic lubricant, because wish in the synthetic lubricant mixture, the molecular weight distribution of component can be simulated the molecular weight distribution of mineral oil under their dispersity index (being the standard error curve), so that the mixing gradually of component in continuity and the product mixtures is arranged.By above-mentioned be that the molecular weight distribution of the product that obtains of the individual elements of 10 multiple does not resemble the standard error curve, therefore, owing to there is not the mixing gradually of continuity and closely-related oligopolymer, product lacks the stable of character.That is,, make mixture lack stable character owing to there is not the mixing gradually of the oligopolymer of continuity and closely-related/adapt.In addition, it is somewhat expensive using purer monoolefine.Make the olefin product that obtains by Fischer-Tropsch synthesis oligomeric, then hydrogenation or isomerized oligomer form lubricating oil method (referring to, the Monoolefins of F Asinger for example, Chemistry﹠amp; Technology, 900 and 1089 pages (1968), Pergamon Press publishes) also be known.Yet, relate to and use the fischer-tropsch product not illustrate that as these publications of the raw material of oligomerization step product mixtures requires required oligopolymer that obtains or the catalyzer that is suitable for oligomerization step.In we formerly disclosed EP-A-0583072; we are claimed and described a kind of method of catalytic oligomerization alkene feed preparation lubricating oil; wherein the alkene charging contains the mixture of C5-C18 alkene, but contains the 1-hexene of 6%w/w at least and the 1-decene of 2.6%w/w at least.Yet the 1-hexene is a kind of valuable monomer, and it has more other purposes of large economy value, for example as producing the particularly poly comonomer of higher polyolefins.

Therefore, the objective of the invention is investigate to select charging, such requirement should be at first satisfied in this charging, can form the product that contains suitable component mixture, and this charging also can be from relatively cheap and commercially available feedstock production.A kind of such charging is the alkene mixture that is obtained by Fischer-Tropsch synthesis, and this charging obtains easily.Yet, only select charging to be not enough to reach this purpose, because the oligomeric condition that also is necessary to determine catalyst system and can accesses suitable oligomer mixture.

At present, have been found that and contain C7-C9 alkene but the commercially available alkene charging of essentially no hexene can be by oligomeric one-tenth oligopolymer that this oligopolymer can have the character of those oligopolymer that obtained by the charging that contains hexene.

Therefore, the present invention be the preparation viscosity index at least 120 and pour point be the method for-45 ℃ or lower lubricating oil.This method comprises that (a) lower polyolefins charging in the presence of the oligomerisation catalyst that contains alkyl aluminum halide and alkylogen forms lubricating oil, (b) lubricating oil is separated with oligomerisation catalyst, (c) in the presence of hydrogen, selectively make the lubricating oil shortening to improve its oxidative stability and (d) to reclaim the lubricating oil of formation like this, it is characterized in that the essentially no hexene of i. alkene charging and comprise the mixture of the alkene that contains 7-9 carbon atom, as defined herein, the amount of heptene is 30%w/w at least in this charging, and the mol ratio of alkylogen and alkyl aluminum halide is 1.0 in the ii. oligomerisation catalyst: 1-20: in 1 scope and the iii. oligomerization at 50 ℃ or be lower than under 50 ℃ the temperature and carry out.

The alkene charging is substantially free of hexene, i.e. charging contains the hexene of no more than 2%w/w, suits to be less than 1%w/w, preferably is less than 0.5%w/w, and comprises the mixture of the alkene that contains 7-9 carbon atom.In this mixture, the amount of heptene is 30%w/w at least, and contains octene and/or nonene.The alkene charging beyond octene and/or the nonene, also can contain other alkene except containing heptene, butylene for example, amylene, decene or higher alkene more, preferred 1-decene, but the amount of heptene is a heptene in this mixture in the palpus mixture, the 30%w/w at least of octene and nonene total amount.The amount of heptene is preferably 40-75%w/w in this mixture, more preferably 45-70%w/w.Alkene, particularly heptene in the common used alkene charging, octene and nonene be 1-alkene preferably.The more preferred example of this charging is the olefin stream that is formed by Fischer-Tropsch synthesis, the weight percent that this Fischer-Tropsch synthesis is operated by this way so that the alkene charging that obtains contains its 1-alkene separately is at 40-45: 30-35: the C7 in the 20-25 scope, the mixture of C8 and C9 1-alkene.For example be known that " Monoolefins, the Chemistry﹠amp of the F Asinger that publishes at Pergamon Press; Technology ", the gasol that is obtained by FTS described in 1089 pages (1968) contains 50% but-2-ene of having an appointment, and it is said that this gasol obtains the lubricating substance of difference with the aluminum chloride polymerization time.Therefore, any product mixtures that does not limit of the FTS that does not limit is not suitable as the charging of the inventive method very much.

Usually, in Fischer-Tropsch synthesis (hereinafter claiming " FTS "), the mixture of carbon monoxide and hydrogen forms various hydrocarbon by the catalyst bed of heating.When hydrogen richness was high in the reaction mixture, reaction product mainly contained paraffinic hydrocarbons.Yet when if the ratio of hydrogen is low in the reaction mixture, reaction product mainly contains alkene.Yet even may mainly be under the situation of alkene in the reaction product of FTS, the reaction conditions that also must control FTS be to obtain required heptene, the mixture of octene and/or nonene.

Used oligomerisation catalyst is the mixture of alkyl aluminum halide and alkylogen.Therefore, the suitable general formula R of using of alkyl aluminum halide _nAlX _3-nExpression, wherein R is the primary of C1-C4, the second month in a season or tertiary alkyl, preferably uncle or secondary alkyl are more preferably alkyl aluminum halide (hereinafter claiming " AAH "); X is a halogen atom, can be chlorine, bromine or iodine, preferred chlorine; N is the integer of 1-3, preferred 1-2.The alkylogen component of this catalyzer is fit to have formula R ₃X, wherein R has and last identical implication with X, and preferably tertiary alkyl such as tertiary butyl chloride (hereinafter claiming " TBC ").AAH is ethylaluminium dichloride (hereinafter claiming " EADC ") preferably.Alkylogen in the oligomerisation catalyst is 1.0 with the relative mol ratio of AAH: 1-20: 1, preferred 2.5: 1-15: 1.

The accurate content of selected two catalyst components will depend on the desired specific nature of final lubricating oil, for example viscosity.

Oligomerization is at 50 ℃ or is lower than under 50 ℃ the temperature and carries out, is fit at room temperature carry out, and for example 15-50 ℃, preferably about 0-30 ℃.Used reaction pressure can be a normal pressure.

Oligomerization is adapted at being under the reaction conditions under the existence of inert solvent and carries out preference chain alkane such as normal hexane.

Preferably, earlier the TBC of aequum is joined in the alkene charging in inert solvent, and the temperature of this solution is elevated to temperature of reaction, then AAH solution (preferably in identical inert solution) is dropwise joined in for some time in the solution of alkene charging and TBC under continuously stirring.Again through after a while, for example come the neutralization reaction mixture after EADC solution adds, wash then and filter by adding ammonia.Can make inertialess solvent in the organic product by for example evaporation then.If necessary, above-mentioned steps can be carried out under operate continuously.

The residue that obtains is an oligopolymer, and this oligopolymer is to have lubricating oil important and required character, but it can contain a spot of olefin component.

An importance of the present invention is by charging, oligomerisation catalyst and the oligomerization condition of selecting to be fit to, and makes to guarantee that oligopolymer has considerably less olefin group, thereby has avoided the needs to the optional hydrogenation step of postorder basically.

Hydrogenation step (when using) can compatibly carry out to guarantee that any olefin group in the oligopolymer all is saturated, and the effect of this step is to improve the oxidation of lubricating oil stability that forms in the step (b).Under situation of the present invention, hydrogenation step can use the hydrogenation catalyst of any routine, for example other metals of the VII of Raney nickel or Mendeleev chart or VIII family.This step is carried out in the presence of hydrogen, and its reaction pressure (comprising the hydrogen dividing potential drop) is suitably for 20-1000KPa, preferred 350-750KPa.Hydrogenation reaction is adapted at carrying out in the 0-350 ℃ of temperature range.

With known method as the distillation with hydrogenation products and catalyzer and any separation of by-products.

Hydrogenation products of the present invention is fabulous lubricant, and it can be used as lubricant or is used for mixing with other additives of lubricating oil.The pour point of the product of the inventive method can be lower than-45 ℃ and viscosity index and be higher than 120.

Further specify the present invention with reference to the following example.Embodiment 1

(80 restrain with the 1-heptene in storage tank, 0.815 mole), 1-octene (10 grams, 0.089 mole) and the mixture of 1-nonene (10 gram, 0.079 mole) mix (total mass 100 of 1-alkene restrains 0.983 mole) with normal heptane (181 restrain), under the rotating speed of about 1000rpm stirs, the 1-alkene mixture solution that obtains is cooled to+16 ℃, in this mixture, add tertiary butyl chloride (TBC initiator, 6 grams, 0.065 mole).

Then under agitation will be in 15 minutes at ethylaluminium dichloride (the EADC catalyzer among " hexane " (available from Aldrich Chemicals), 0.020 solution (1M mole), 20 milliliters) dropwise join in 1-alkene mixture/TBC solution, temperature of reaction is elevated to about 28 ℃ by 12 ℃ during this period, and the initiator in this reaction mixture is 3.5 with the ratio of catalyzer.

After beginning to add EADC oligomerization was carried out 2 hours, make reaction terminating by 1-2 minute catalyst deactivation of anhydrous ammonia gas bubbling, after adding ammonia, add 100 ml water washing reaction mixtures, 180 ℃ with the decompression under by rotary evaporation washed reaction mixture is separated with lightweight polymeric with solvent.

The material that evaporation stays is a lubricating oil, and corresponding yield is 75%w/w (being calculated by 1-alkene).This oily dynamic viscosity is 141.1cSt (under 40 ℃) and 16.37cSt (under 100 ℃), viscosity index be 123 and pour point be-48 ℃.Embodiment 2

The reactant solution that uses the method identical with the foregoing description 1 to prepare carries out another embodiment.

As above-mentioned embodiment 1, under agitation will contain 100 solution that restrain alkene mixtures (0.983 mole) to be cooled to+16 ℃, the add-on of TBC initiator is 9 grams (0.097 mole).To dropwise join with the EADC solution of embodiment 1 same concentrations in 1-alkene mixture/TBC solution, but the ratio of initiator in the present embodiment and catalyzer is 5.0.As the foregoing description 1 reaction is carried out, and the aftertreatment reaction product.The oil that obtains (yield 68.1%w/w) has following character: dynamic viscosity (under 40 ℃) is 99.01cSt and 12.50cSt (under 100 ℃), viscosity index be 120 and pour point be-48 ℃.

Claims (13)

1. One kind prepare viscosity index at least 120 and pour point be the method for-45 ℃ or lower lubricating oil, this method comprises that (a) lower polyolefins charging in the presence of the oligomerisation catalyst that contains alkyl aluminum halide and alkylogen forms lubricating oil, (b) lubricating oil is separated with oligomerisation catalyst, (c) in the presence of hydrogen, selectively make the lubricating oil shortening with improve its oxidative stability and (d) recycling step (b) or (c) in the generation lubricating oil, it is characterized in that the essentially no hexene of i alkene charging and comprise the mixture of the alkene that contains 7-9 carbon atom, as defined herein, the amount of heptene is 30%w/w at least in this charging, and the mol ratio of alkylogen and alkyl aluminum halide is 1.0 in the ii oligomerisation catalyst: 1-20: in 1 scope and the iii oligomerization at 50 ℃ or be lower than under 50 ℃ the temperature and carry out.
2. 2. according to the process of claim 1 wherein that the alkene charging contains the hexene of no more than 2%w/w and the amount of heptene is 40-75%w/w.
3. 3. according to the method for claim 1 or 2, wherein the alkene in the alkene charging is 1-alkene.
4. 4. according to the method for above-mentioned each claim, wherein the alkene charging is the olefin stream that is formed by Fischer-Tropsch synthesis, the weight percent that this Fischer-Tropsch synthesis is operated by this way so that the alkene charging that obtains contains its 1-alkene separately is at 40-45: 30-35: the C7 in the 20-25 scope, the mixture of C8 and C9 1-alkene.
5. 5. according to the method for above-mentioned each claim. alkyl aluminum halide general formula R wherein _nAlX _3-nExpression, wherein R is the primary of C1-C4, the second month in a season or tertiary alkyl, X are halogen atoms, can be chlorine, bromine or iodine, preferred chlorine; N is the integer of 1-3.
6. 6. according to the method for above-mentioned each claim, wherein alkyl aluminum halide is an ethylaluminium dichloride.
7. 7. according to the method for above-mentioned each claim, wherein the alkylogen in the catalyzer has formula R ₃X, wherein R is the primary of C1-C4, the second month in a season or tertiary alkyl, X are halogen atoms, can be chlorine, bromine or iodine.
8. 8. according to the method for above-mentioned each claim, wherein alkylogen is a tertiary butyl chloride.
9. 9. according to the method for above-mentioned each claim, wherein the alkylogen in the oligomerisation catalyst and the relative mol ratio of alkyl aluminum halide are 2.5: 1-15: in 1 scope.
10. 10. according to the method for above-mentioned each claim, wherein oligomerization is to carry out under 15 ℃ of-50 ℃ of temperature.
11. 11. according to the method for above-mentioned each claim, wherein oligomerization is to be in the presence of the inert solvent to carry out under reaction conditions.
12. 12. according to the method for above-mentioned each claim, wherein when using hydrogenation step, hydrogenation step is to carry out under use is selected from the condition of hydrogenation catalyst of the VII of Raney nickel or Mendeleev chart or other metals in the VIII family.
13. 13. according to the method for claim 12, wherein hydrogenation step be in the presence of hydrogen, reaction pressure (comprising the hydrogen dividing potential drop) carries out under the condition in 0-350 ℃ of scope at 20-1000Kpa and temperature.