CN101356257A

CN101356257A - Base oil

Info

Publication number: CN101356257A
Application number: CNA2006800466560A
Authority: CN
Inventors: P·阿尔托; J·莫伊莱南; J·约基南; E·科伊乌萨尔米; J·米尔约加; J·加库拉; V·尼米
Original assignee: Neste Oyj
Current assignee: Neste Oyj
Priority date: 2005-12-12
Filing date: 2006-12-12
Publication date: 2009-01-28
Anticipated expiration: 2026-12-12
Also published as: FI20055662A0; ZA200804738B; DK1966357T3; TR201908714T4; HUE043719T2; FI20055662A; BRPI0619604A2; ES2731850T3; PT1966357T; CN101356257B; MY147368A

Abstract

The invention relates to a new base stock material. Specifically the invention relates to a saturated hydrocarbon composition and particularly to a composition based on biological raw materials, to be used as a high-quality base oil or to be used as a component in the production of a base oil having a high viscosity index and good low temperature properties. The composition contains saturated hydrocarbons and has a narrow carbon number range.

Description

Base oil

Technical field

The present invention relates to a kind of new oil base stock material.Particularly, the present invention relates to a kind of branched-chain saturated hydrocarbon composition and be particularly related to a kind ofly based on the raw-material composition of biology, it is suitable as the high quality base oil or is used as component in production has the base oil of high viscosity index (HVI) and good low-temperature performance.Said composition contains branched-chain saturated hydrocarbon, and it has narrow carbon number range.

Prior art

Base oil is generally used for making lubricant, for example automobile lubricating oil, industrial lubricants and lubricating grease.They are also as process oil, white oil and metalworking fluid.Finished lubricants is made of two kinds of parts commonly used, and this part commonly used is lubricating base oil and additive.Base oil is the main component in the finished lubricants, and they significantly help the performance of finished lubricants.Usually, some base oils are used for making multiple finished lubricants by the mixture that changes single base oil and independent additive.American Petroleum Institute (American Petroleum Institute (API)) (API) base oil is sorted in shown in the table 1.Nowadays, the III of API and IV group base oil is used for the high quality lubricant.

The classification of table 1.API base oil

The oil of III group is for having the base oil of pole height viscosity index (VHVI), and it by hydrocracking, is produced branched paraffin by the isomerization of wax straight-chain paraffin subsequently and produce by crude oil by modernism.The oil of III group also comprises by from (SW) base oil produced of paraffinic hydrocarbons of the waxy stone (Slack Wax) of mineral oil.Use corresponding isomerization technique, synthetic by Fischer-Tropsch (FT), for example the following product of the wax that is obtained by coal or Sweet natural gas (GTL wax) manufacturing also can belong to this group in the future, and described following product is still unavailable now.The oil of IV group is synthesizing poly alpha-olefin (PAO).The ester base oil that belongs to the V group is produced by lipid acid and alcohol.Described lipid acid is natural or synthetic list or dicarboxylic acid.According to the ester that will produce, alcohol is polyvalent alcohol or single hydroxyl alcohol.Ester base oil is generally monoesters, diester, polyol ester or dipolymer ester.Similarly classification is also by ATIEL (Association Technique de l ' Industrie Europ é enne des Lubrifiants, or Technical Association of the European Lubricants Industry) use, described classification also comprises the VI group: poly-internal olefin (Polyinternalolefin) (PIO).Except that official classification, the II+ group also is generally used for this area, and this group comprises viscosity index greater than 110, but is lower than 120 saturated and no sulphur base oil.In these classification, stable hydrocarbon comprises paraffinic hydrocarbons and alicyclic hydrocarbon compound, but does not comprise aromatic hydroxy compound.

According to API 1509, also can use as giving a definition: " the lubricant composition of oil base stock for producing according to same size (irrelevant) with raw material sources or manufacturers place by single manufacturers for base oil (oil base stock); It satisfies identical manufacturers's standard; And identify by unique chemical formula, product identification number or both.Oil base stock can be used various method manufacturing ".Base oil is oil base stock or the oil base stock blend that is used for the API concession oil.The oil base stock type is 1) mineral oil (paraffinic hydrocarbons, alicyclic hydrocarbon, aromatic hydrocarbons), 2) synthetics (poly-alpha olefins, alkylated aromatic hydrocarbons, diester, polyol ester, polyalkylene glycol, phosphoric acid ester, siloxanes) and 3) vegetables oil.

Especially, automotive industry has needed lubricant and base oil thus to have the processing performance of improvement for a long time.The standard of finished product top (top-tier) lubricant needs product to have excellent low-temperature performance and low volatility and suitable levels of viscosity day by day.Common top lubricating base oil is that the kinematic viscosity (KV100) under 100 ℃ is about 3cSt or higher; Pour point (PP) is-12 ℃ or still less approximately; And viscosity index (VI) is about 120 or higher.Except that low pour point (PP), need many grades engine oil to have low-temperature fluidity equally, to guarantee that engine starts easily under cold condition.Low-temperature fluidity is expressed as (CCS) apparent viscosity in testing of under-5 to-40 ℃ temperature cold post-start simulation (coldcranking simulation).KV100 should have the CCS viscosity (CCS-30) that is lower than 1800cP under-30 ℃ usually for the modern top base oil of about 4cSt, and KV100 is that the oil of about 5cSt should have the CCS-30 that is lower than 2700cP; This value is low more good more.Usually, lubricating base oil should have the Noack volatility that is not more than existing conventional I group or II group lightweight neutral oil.At present, only the base oil of sub-fraction manufacturing can be used to satisfy the formulation of up-to-date, most of required lubricant standards.

Mineral base oil (the APII group also is the II group sometimes) by routine no longer may be produced and satisfy the lubricant that great majority require automaker's standard.Usually, described oil often contains aromatic hydrocarbons, sulphur and the nitrogen compound of excessive concentrations, and further, they also have the viscosity index of high volatile volatile and difference.In addition, mineral oil is often appropriate for the response of antioxidant addn.

Synthetic (PAO; The IV of API organizes) and so-called semi-synthetic base oil (VHVI; The III of API group) in the automotive lubricant of for example engine and gear oil, plays the part of important role day by day especially.The time limit of service of lubricant is desirably long as far as possible, avoid thus the frequent maintenance shop of changing oil and further can prolong the vehicle in the commercial transport instrument for example of user every.In the past decade, the engine oil change of passenger car has improved five times at interval, mostly is 50 most, 000km.For heavy vehicle, engine oil change has been in 100, the level of 000km at interval at present.Can see similarly " more long lifetime " progress in industrial lubricants.

By oligomeric 'alpha '-olefin monomers, then hydrogenation obtains complete paraffinic hydrocarbons base oil and makes synthetic PAO type base oil.The PAO base oil has higher VI value and simultaneously excellent low-temperature performance, PP even be lower than-60 ℃.Because accurate product distillation, the volatility of product is low and flash-point is high.Because the limited operability of expensive raw material alpha-olefin, the production of PAO base oil and application are subjected to suitable restriction.

By removing undesirable compound, by the strict purified base oil of crude production VHVI type.Most crucial steps perhaps is converted into liquid isoparaffin with described n-paraffin for dewaxing, expression removes solid, long chain paraffins by modern technologies.The GTL base oil is made by the synthetic FT wax of isomerization catalysis.Compare with mineral oil, VHVI base oil product is more paraffinic hydrocarbons and has narrower boiling range to have significantly higher VI thus, lower volatility and obviously better low-temperature performance.The aromaticity content of described oil is very low and further, their essentially no sulphur and no nitrogen.

Except that the industrial requirement of vehicular engine technology, strict environmental requirement makes the base oil that industrial development is more complicated equally.Need sulfur free fuel and base oil, so that obtain whole effects of catalyst technology new in the modern vehicle and interrupt oxynitride, volatile hydrocarbon and particulate discharging, and the direct reduction that realizes the sulfurous gas in the waste gas.Conventional mineral oil contains sulphur, nitrogen, aromatic substance, and than the no sulphur base oil that upgrades, and conventional mineral oil is normally more volatile and be more deleterious on the environment therefore.In addition, mineral oil is not suitable for having the new engine of sensitive catalyst material.

The production of base oil too is subjected to common day by day " life cycle evaluation " (LCA) influence of method.The target of LCA is to check the carrying capacity of environment of product " from giving birth to till death ".LCA is the time limit of service of seeking stagnation point and can prolonging product, and makes production, application, processing and the discarded relevant minimized means of environmental drawbacks with product.The oil change interval of high quality base oil is long to make the consumption of non-renewable mineral crude oil based raw material reduce, and the amount of Hazardous wastes petroleum products is reduced.

Now, using refiltered oil and renewable raw materials in the lubricant manufacturing often is the target of being considered.In the hydrocarbon component is produced, use the renewable raw materials of biogenetic derivation but not non-renewable fossil feedstock to produce the hydrocarbon component be ideal because fossil feedstock can be exhausted and their greenhouse gases (GHG) be deleterious to the influence of environment.The problem relevant with refiltered oil is included as purification and the reprocessing step complexity that obtains having high-quality base oil.In addition, the research and development of operation and large-scale recovery logistic system are expensive.

Up to now, ester has been the base oil types that is used for the only renewable and biogenetic derivation of lubricant.The use of described ester is limited to some special applications, for example loop check (chain-saw) oil, biological hydraulic efficiency oil and metalworking fluid.In general-utility car and industrial lubricants, ester is mainly as additive.High price has also limited the use of ester.In addition, even substitute therein under the on all four basically situation of chemical constitution of ester, under the condition of not carrying out expensive Engine Block Test once more, the ester that is used for the engine oil formulation also can not with other ester interchange.As an alternative, the base oil that is made of pure hydrocarbon structure can part exchange each other.Also have some technical problems relevant with ester.As polar compound, ester stands the sealing bigger than pure hydrocarbon-swelling tendency.This point has produced some problems relevant with the elastomerics in the hydraulic applications.In addition, the easier hydrolysis of ester base oil produces acid, itself so that cause the oiling system corrosion.In addition, the bigger shortcoming of ester be for the additive of non-polar hydrocarbon base oil exploitation invalid to the polarity ester base oil.

A kind of method with two steps of FI 100248 expressions wherein by the carboxylic acid of vegetables oil or the hydrogenation of tri-glyceride, produces linear straight chain alkane, and then the isomerization by described n-paraffin obtains branched paraffin, by vegetable oil production middle runnings.Hydrogenation is at 330 to 450 ℃, is higher than under the pressure of 30 crust and 0.5 to 5l/h the liquid hourly space velocity (LHSV) to carry out.Isomerization steps carries out under the LHSV of high pressure and 0.1 to 10l/h at 200 to 500 ℃.

EP 774451 discloses the method for a kind of isomerization lipid acid or fatty acid alkyl ester.Use clay or another kind of cationic catalyst to carry out the isomerization of unsaturated fatty acids or fatty acid alkyl ester.Except primary product, also obtain the raw material dipolymer.After the distillation, obtain unsaturated branching lipid acid or fatty acid alkyl ester as product.

GB 1 524 781 discloses a kind of method by the vegetable oil production hydrocarbon.In the method, the vegetables oil raw material is at 300-700 ℃, in the presence of catalyzer, and pyrolysis in three zones.In the method, obtain carburet hydrogen, gasoline and diesel oil classification.Their separated and purifications.

EP 209997 discloses a kind of method of production basis oil, comprises the waxy hydrocarbon of isomerization based on crude oil, produces only a spot of light ends.This method is used to for example be belonged to by the wax bottoms production of hydrocracking the base oil of III group.

The PAO method is documented in many patents.US 6,703, and 356 disclose a kind of method of using the macrovoid crystalline catalysts in by 1-olefinic monomer production PAO base oil, and described 1-olefinic monomer is usually by former oil base ethylene production.This patent is described and is replaced normally used C10 (1-decene) or C8-C12 alpha-olefin mixture, uses the high alpha-olefin monomer, and preferred C14 to C18 alpha-olefin is as starting material.After alpha-olefin is oligomeric, product is distilled to required viscosity fraction, hydrogenation subsequently obtains saturated " star " paraffinic hydrocarbons.

US 2005/0133408 discloses a kind of base oil composition, contains the naphthenic hydrocarbon greater than 10wt%, and monocycle alkane greater than 15, further contains the aromatic substance that is less than 0.3wt% to the ratio of polycyoalkane.Make by the synthetic isolating paraffin wax that obtains of Fischer-Tropsch by hydroisomerization to dewax, and carry out hydrofining at last and obtain said composition.

FI 66899 describes and uses fatty acid triglyceride and polymkeric substance thereof as the lubricant base oil.Because oxidation and hydrolysis cracking, the two keys and the ester bond of final product are unsettled.Described disclosed base oil comprises unsaturated ester.

EP 03396078 provides a kind of Dresel fuel compositions that contains biological components, described composition comprises at least a component of being produced by the biological starting material in plant, animal or fish source, based on crude oil and/or from the diesel component and the optional component that contains aerobic of the fraction of Fischer-Tropsch method.

Use biogenetic derivation contain heteroatomic starting material up to now report be used to produce saturated base oil of high quality or base oil component.

Based on above instruction, can find to have conspicuous demand for the base oil and the base oil component of biogenetic derivation, described oil contains the branching paraffinic hydrocarbons, and further satisfy the extra good quality requirement of base oil, compare with conventional mineral base oil, described oil is to environment, to final user and more favourable to the influence of the saving of non-renewable raw material, and described base oil is technical to be better than present prior art product.

Goal of the invention

Goal of the invention provides a kind of novel saturated base oil or base oil component.

Further goal of the invention is based on the base oil or the base oil component of the raw material of biogenetic derivation.

Further goal of the invention is based on the base oil or the base oil component of the raw material of biogenetic derivation, and described base oil or component satisfy the II+ group for API, the specification of quality of the t base oil of preferred III group.

Another goal of the invention provides saturated base oil or the base oil component based on the raw material of biogenetic derivation, compares with the base oil based on crude oil of routine, and described oil or component are more favourable to the influence of the saving of environment, final user and non-renewable raw material.

According to the present invention, in claims, provide based on the base oil of the raw material of biogenetic derivation or the feature of base oil component.

Summary of the invention

According to the present invention, mainly comprise saturated branched-chain hydrocarbon based on the base oil or the base oil component of the raw material of biogenetic derivation, its carbon number range is narrower than the carbon number range of the product overhead product that is obtained by traditional method.Described base oil or base oil component satisfy the II+ group of API, the specification of quality of preferred III group.

Paraffinic hydrocarbons and alicyclic hydrocarbon compound represented in term " stable hydrocarbon " as used herein, but do not represent aromatic hydroxy compound.Paraffin compound can be branching or linear.Alicyclic hydrocarbon compound is cyclic saturated hydrocarbon, i.e. naphthenic hydrocarbon.This hydrocarbon with ring texture is generally the derivative of pentamethylene or hexanaphthene.Alicyclic hydrocarbon compound can comprise single ring architecture (monocycle alkane) or two isolating ring structures (isolating bicyclic alkane), or two condensed ring structures (fused bicyclic alkane), or three or more condensed ring structures (polycyclic naphthene hydrocarbon or polycyoalkane).

Here, the term polyvalent alcohol represents to have the alcohol of two or more hydroxyls.

Here, the maximum carbon number of molecule and the difference of minimum carbon number add one in the carbon number range width means the finished product.

Here, lipid acid represents that carbon number is higher than the carboxylic acid of the biogenetic derivation of C1.

Here, pressure is the gauge pressure with respect to standard atmospheric pressure.

Detailed Description Of The Invention

Find surprisingly to comprise that carbon number is that C18 can be by the starting material production of biogenetic derivation with saturated high quality base oil or base oil component with branched-chain saturated hydrocarbon of narrow carbon number range at least, described oil or component are equivalent to the II+ group of API, the base oil of preferred III group qualitatively.According to the present invention, the base oil of biogenetic derivation or the boiling range of base oil component (ASTM D 2887) begin to be higher than 250 ℃, and carbon number range and boiling spread are very narrow, and further, viscosity index is very high and low-temperature performance is good simultaneously.According to the present invention, the base oil of biogenetic derivation or base oil component contain the stable hydrocarbon of 90wt% at least, and the ratio of straight-chain paraffin is less than 10wt%.

The carbon number range width of base oil of the present invention or base oil component is less than nine carbon usually.The typical carbon number range and the typical structure of base oil of the present invention provide in following table 2, and most typical carbon number is the runic form.

The carbon number of base oil of the present invention or base oil component and carbon number range depend on as the biological starting material of raw material and further depend on production method.In the structure example of table 2, base oil component of being produced by ketonization by the C16/C18 raw material 1 and 2 carbon number range are generally C31 to C35 and the carbon number range of the base oil component 3 produced by condensation by the C16/C18 raw material is generally C32 to C36.These all represent the modal carbon number distribution of five carbon atoms.The raw material that comprises single fat acid chain length produces very narrow carbon number range.

The biological basis oil ingredient of the present invention that provides in the table 2 is with following described method production.

1. ready denier oil acid carries out isomerization generation branched product, carries out ketonization subsequently and carries out hydrogenation at last.

2. the Zoomeric acid fraction carries out ketonization, carries out hydrogenation subsequently and carries out isomerization at last.

3. plam oil C16 lipid acid overhead product carries out condensation, carries out hydrogenation subsequently and carries out isomerization at last.

Table 2

The structure of the base oil/component of biogenetic derivation

Have the carbon number of known synthetic hydrocarbon base oil of mineral base of similar levels of viscosity and theoretical typical structure shown in the table 3.Carbon number range is by the FIMS assay determination.The structure of naphthenic hydrocarbon is the representative instance of one group of compound.

Table 3

The typical structure of known base oil

The common following production of the product of table 3:

1. use homogeneous catalyst is by the oligomeric PAO C10 that is produced by 1-decene

2.SW be the isomerization product of the waxy stone fraction of mineral oil based.

3.VHVI be hydrocracking and isomerization base oil derived from mineral oil.

According to carbon and hydrogen atom, below use FIMS method (field ionization mass spectrometry) that stable hydrocarbon is categorized as:

1 C (n) .H (2n+2) paraffinic hydrocarbons

2 C (n) .H (2n) monocycle alkane

3 C (n) .H (2n-2) bicyclic alkane

4 C (n) .H (2n-4), three naphthenic hydrocarbon

5 C (n) .H (2n-6) Fourth Ring alkane

6 C (n) .H (2n-8) five rings alkane

In the table 2 and 3, per-cent (% is by FIMS) expression is according to the group of the compound of described method mensuration.

With regard to molecular structure, base oil of the present invention or base oil component are different from the product of prior art, shown in table 2 and 3.Prior art PAO base oil mainly comprises long (＞4 carbon) alkyl branches (structure 1 in the table 3).In the SW of prior art isomerization product (structure 2 in the table 3), short-chain branch is usually at the end of hydrocarbon skeleton.Base oil of the present invention or base oil component in the table 2 shown in the structure 2 and 3 are very similar to the SW base oil, but the SW base oil contains significantly more the monocycle alkane and the fused bicyclic alkane of a large amount.

When carrying out isomerization (structure 1 in the table 2) based on the lipid acid skeleton, there is 1 to 4 carbon alkyl branches in the product hydrocarbon chain usually.The branching component is the different mixture of isomers of branch position.

Compare the side chain at chain end place, hydrocarbon intrachain side chain reduces pour point more significantly.Except the side chain position, its number influences pour point.Along with the side chain number increases, depression of pour point causes viscosity index to reduce simultaneously.In product of the present invention, the isomerization molecule of higher proportion contains more than 30 carbon atoms.Even pour point (PP) is lower than-20 ℃, this macromolecular compound also shows high VI usually.

As the result of cracking and hydrogenation polynuclear aromatic compound, in the VHVI of prior art product, also have condensed polycyoalkane (structure 3 in the table 3), but it is not present in the product of the present invention with 3-5 ring.Fused rings alkane makes the PP-VI relation than alkyl branches difference.By optimizing the side chain number of appropriate position, can obtain best PP-VI relation.

The product of the present invention (structure 2 in the table 2) that is obtained by the paraffin isomerization from hydrogenation deoxidation ketone is branched product, and it has lower methyl branch amount and have more methyl or ethyl branch in hydrocarbon skeleton in the hydrocarbon chain end.Described base oil generally includes some monocycle alkane, but does not have fused bicyclic alkane also not have polycyoalkane.Described monocycle alkane forms as the reaction of the two keys of fatty acid carbon chain or the result of isomerization reaction, so its structure is different with the naphthenic hydrocarbon that is obtained by the polycyoalkane cracking in aromatic hydrocarbons hydrogenation and the mineral oil.

Use comprises main hydrocarbon chain intermediary methyl branch (structure 3 in the table 2) according to the condensation reaction of aldol condensation, pure condensation (Guerbet reaction) or the product that free radical method obtains.This product is different from the VHVI and the SW isomerization product (structure 3 and 2 in the table 3) of prior art, and described oil mainly has side chain at chain end usually.

Base oil of the present invention or base oil component comprise the product of being produced by the starting material of biogenetic derivation, and described product contains and is less than 10wt%, preferably are less than 5wt% and especially preferably are less than the straight-chain paraffin of 1wt%; At least 90wt%, preferably 95wt% and especially preferably 97wt% at least at least, the stable hydrocarbon of 99wt% at most at least are as by gas-chromatography (GC) assay determination.

Product of the present invention contains by FIMS, 5-50%, preferred 5-30%, the monocycle alkane FIMS of preferred especially 5-15% and best 5-10%; With by FIMS, be less than 0.1% polycyoalkane FIMS, as measuring by the FIMS method.

For described base oil or base oil component, VI is greater than 115 and be preferably greater than 130, is preferably greater than 140 especially, with more preferably greater than 150, as measuring by the method for ASTM D 2270 and pour point is no more than-9 ℃, preferably be no more than-12 ℃ and especially preferably be no more than-15 ℃ (ASTMD 5950).

The low temperature movement viscosity of described base oil or base oil component, CCS-30 is 29.797* (KV100) at the most ^2.7848CP, preferably 34.066* (KV100) at the most ^2.3967CP; CCS-35 is 36.108* (KV100) at the most ^3.069CP, preferably 50.501* (KV100) at the most ^2.4918CP is measured by ASTM D 5293 methods; Pour point is lower than-9 ℃, preferably is lower than-12 ℃ and especially preferably be lower than-15 ℃ (ASTM D 5950).

For described base oil or base oil component, KV100 is the volatility 2271.2* (KV100) at the most of the product of 3cSt to 8cSt ^-3.5373Wt% is as being measured by DIN 51581-2 method (based on ASTM D 2887 GC distillatory Mathematical Noack methods).

The carbon number range of base oil of the present invention or base oil component is 9 carbon at the most, preferred 7 carbon at the most, and especially preferably 5 carbon and preferably 3 carbon at the most at the most are as being measured by the FIMS method.Surpass about 50wt%, the base oil that preferably surpasses about 75wt% and preferred especially about 90wt% of surpassing contains the hydrocarbon that belongs to this narrow carbon number distribution.

The boiling range of base oil of the present invention or base oil component is 150 ℃ at the most, preferably at the most 100 ℃, and especially preferably 70 ℃ and preferably 50 ℃ (method by ASTM D 2887 is measured, and heating up in a steamer point (distillation point) is D10 and D90) at the most at the most.

The sulphur content of described base oil or base oil component is lower than 300ppm, preferably is lower than 50ppm, especially preferably is lower than 10ppm and most preferably less than 1ppm, as what measured by the method for ASTM D 3120.

The nitrogen content of described base oil or base oil component is lower than 100ppm, preferably is lower than 10ppm and especially preferably is lower than 1ppm, as being measured by the method for ASTM D 4629.

Described base oil or base oil component contain carbon ¹⁴The C isotropic substance, it can be considered to use the indication of renewable raw materials.The typical case of the total carbon content in the product of complete biogenetic derivation ¹⁴The C isotopic content is at least 100%.Carbon ¹⁴C isotopic content (ratio) depends on the radiocarbon C14 (carbon in the nineteen fifty atmosphere ¹⁴The C isotropic substance) basis of content (ASTM D 6866).Except that biological components other component is used under the situation of processed products therein, base oil of the present invention ¹⁴The C isotopic content is lower, but described content surpasses 50%, preferably surpasses 90%, especially preferably surpasses 99%.In this way, in other alkyl oil type, can detect even the base oil of a spot of biogenetic derivation.

Base oil of the present invention or base oil component can origin come from the raw-material feedstock production of biogenetic derivation, and described raw material is called as biological starting material in this manual.These biology starting material are selected from:

A) vegetation fat, vegetables oil, vegetable wax, animal tallow, animal oil, animal wax, fish fats, fish oil, fish wax and

B) by hydrolysis, transesterify or pyrolysis by vegetation fat, vegetables oil, vegetable wax; Lipid acid that animal tallow, animal oil, animal wax, fish fats, fish oil, fish wax and composition thereof obtain or free fatty acids and

C) ester that obtains by vegetation fat, vegetables oil, vegetable wax, animal tallow, animal oil, animal wax, fish fats, fish oil, fish wax and composition thereof by transesterify and

D) by saponification by vegetation fat, vegetables oil, vegetable wax, animal tallow, animal oil, animal wax; The metal-salt of the lipid acid that fish fats, fish oil, fish wax and composition thereof obtain and

E) from the acid anhydrides of the lipid acid of vegetation fat, vegetables oil, vegetable wax, animal tallow, animal oil, animal wax, fish fats, fish oil, fish wax and composition thereof and

F) ester that obtains by the esterification of the free fatty acids in plant, animal and fish source and alcohol and

G) Fatty Alcohol(C12-C14 and C12-C18) that obtains as reduzate or aldehyde from the lipid acid of vegetation fat, vegetables oil, vegetable wax, animal tallow, animal oil, animal wax, fish fats, fish oil, fish wax and composition thereof and

H) food grade fats of Hui Shouing and oil and the fat that obtains by genetic engineering, oil and wax and

I) described raw-material mixture.

Biological starting material also comprise derived from the respective compound of algae and insect and derived from the aldehyde that is prepared by carbohydrate and the starting material of ketone.

Suitable biological raw-material example comprises fish oil, for example Baltic Sea menhaden fish oil, trout oil, menhaden fish oil, tuna oil, coilia oil, sardine oil and mackerel oil; Vegetables oil, for example rapeseed oil, rapeseed oil, Canola Oil, Yatall MA, wunflower seed oil, soybean oil, Semen Maydis oil, hempseed oil, sweet oil, Oleum Gossypii semen, tori seed oil, plam oil, peanut oil, Viscotrol C, Jatropha seed oil, palm-nut oil and Oleum Cocois; In addition, suitable also have animal tallow, for example lard, butter, and food grade fats and oil discarded and that reclaim, and the fat, wax and the oil that are produced by genetic engineering.Except that fat and oil, the starting material of suitable biogenetic derivation comprise animal wax, for example beeswax, Chinese wax (insect wax), shellac wax (shellac wax) and lanolin (wool wax), and vegetable wax, for example babassu palm wax (carnauba palmwax), ouricouri palm wax, jojoba seed oil (jojoba seed oil), Kan Taili wax (candelilla wax), esparto wax (esparto wax), Japan tallow and Rice pollard oil (rice bran oil).

Biological starting material can also contain free fatty acids and/or fatty acid ester and/or its metal-salt, or biological raw-material cross-linking products.Described metal-salt is generally alkaline-earth metal or an alkali metal salt.

Comprising that carbon number is generally the present invention of at least 18 hydrocarbon or base oil component can be by biological starting material, and (＞C18) method is produced by causing the starting material molecule carbon chain to extend to the base oil desired level.Suitable method comprises the method based on condensation reaction, expression is based on the reaction of raw molecule functionality, itself and following at least a combining: reduction, transesterify, hydrolysis, metathesis, decarboxylation, decarbonylation, isomerization, dewaxing, hydrogenation and process for purification or reaction.Condensation reaction comprises for example decarboxylation condensation (ketonization), aldol condensation, pure condensation (Guerbet reaction) and based on the reaction of two keys, comprises dimerization, trimerization, oligomeric and free radical reaction.Hydrocarbon, preferred stable hydrocarbon obtains as product by processing biological starting material, obtains final product by the described hydrocarbon of distillation fractionation in case of necessity subsequently.

In the method based on the ketonization reaction, the acidic group interreaction of lipid acid produces ketone.Ketonization can also be carried out for fatty acid ester, fatty acid anhydride, Fatty Alcohol(C12-C14 and C12-C18), alkanoic, natural wax and fatty acid metal salt.The ketone that obtains is reduced, and produces paraffinic hydrocarbons, subsequently by isomerization, improves the low-temperature performance of final product.The branching raw material is being carried out under the situation of ketonization, and isomerization is chosen wantonly.In the ketonization step, dicarboxylic acid or comprise that the polyvalent alcohol of dibasic alcohol also can be used as starting material makes that chain can be than only longer with fatty acid prolonging.Under described situation, obtain the polyketone molecule, be processed as monoketone in a similar fashion.In ketonization reaction, pressure is 0 to 10MPa, and temperature is 10 to 500 ℃ and in addition, the metal oxide catalyst of working load, and this metal is preferably molybdenum, nickel-molybdenum, manganese, magnesium, calcium or cadmium; Can use silicon-dioxide and/or aluminum oxide as carrier.In not having the catalyzer of carrier, preferred especially this metal is molybdenum, manganese and/or magnesium in the metal oxide.

In aldolisation, aldehyde and/or ketone condensation significantly increase the carbon number of hydrocarbon stream.Saturated aldehyde is preferably used as raw material.Obtain the unsaturated aldehydes or ketones of branching in the method.Catalyzer is preferably alkalescence or alkaline earth metal hydroxides, for example NaOH, KOH or Ca (OH) ₂, temperature is 80 to 400 ℃, and preferred low temperature and low molecular weight feedstocks are used together, and high temperature and high molecular raw material use together.The amount of catalyzer that is used for homogeneous reaction is by 1 to 20wt%, and preferred 1.5 to 19wt% change.

In pure condensation reaction, particularly in the Guerbet reaction, pure condensation significantly increases the carbon number of hydrocarbon stream, therefore obtains branching simple function and branching polyfunctional alcohol by monohydroxy and polyhydroxy-alcohol respectively in the condensation reaction of alcohol.Saturated alcohol is preferably used as raw material.Known Guerbet catalysts, for example oxyhydroxide of basic metal and alkaline-earth metal and alkoxide, perhaps metal oxide combines with promotor and can be used as catalysts.The amount that is used for catalyst for reaction is by 1 to 20wt%, and preferred 1.5 to 19wt% change.Suitable promotor comprises the salt of chromium (III), manganese (II), iron (II), cobalt (II) or lead (II), or tindioxide or zinc oxide, the salt that salt is water-soluble or pure, preferably sulfuric acid salt.Promotor is with 0.05 to 1wt%, and preferred especially 0.1 to 0.5wt% amount is used.The preferred zinc oxide that uses alkali metal hydroxide and be used as promotor in reaction.The chain extension of the condensation reaction by alcohol is at 200 to 300 ℃, and preferred 240 to 260 ℃ are carried out, and this is reflected under the vapour pressure that is provided by the alcohol that exists in the reaction mixture and carries out.Water disengages in reaction, and described water is separated continuously.

In free radical reaction, the carbochain of saturated carboxylic acid prolongs with alpha-olefin.In the free radical reaction step; comprise that molar ratio is that the raw material of 1: 1 saturated carboxylic acid and alpha-olefin is at 100 to 300 ℃; preferred 130 to 260 ℃; under the vapour pressure that provides by reaction mixture, in the presence of alkyl peroxide, peroxyester, diacyl peroxide or peroxy ketal catalyzer, react.Preferred alkyl peroxide, for example the ditertiary butyl peroxide catalyzer of using.The amount that is used for catalyst for reaction is 1 to 20wt%, and preferred 1.5 to 10wt%.Branched carboxylic acids is used as reaction product and obtains.

In the electrochemical synthesis carboxylic acid, lipid acid in the vegetables oil at first is extracted, subsequently by they are dissolved in contain be useful in and the methyl alcohol or the methanol aqueous solution of the 10-20wt% potassium hydroxide of carboxylic acid, form carboxylate salt, be formed for the electrolyte solution of electrochemical oxidation.This salt is converted into long chain hydrocarbon by being called as the reaction of Kolbe synthetic.The carbon number of products therefrom lacks a carbon than the carbon number that uses the ketonization reaction to obtain.

Make the product that is obtained by the chain extension step be reduced to hydrocarbon (paraffinic hydrocarbons) by hydrogenation, remove the polarity of Sauerstoffatom due to and further thus, oxidative stability is by making any pair of saturated the improving of key.In hydrogenation, the product of chain extension reaction and hydrogen arrive pressure be generally 1 to 15MPa and temperature be 150 to 400 ℃ hydrogenator.In step of hydrogenation, can use the VIII that on carrier, contains the element periodic system and/or the special catalyst of VIA family metal.Hydrogenation catalyst is generally Pd, Pt, Ru, Rh, Ni, NiMo or the CoMo catalyzer of load, and carrier is gac, aluminum oxide and/or silicon-dioxide.After the reduction, by other raw material, rather than the ketonization of not having a branching feed composition obtains the methyl-branched paraffin wax.

The low-temperature performance of product can be improved by isomerization.In isomerization, linear hydrocarbons changes into branched-chain hydrocarbon, and the solid paraffinic hydrocarbons becomes liquid thus.In isomerization, hydrogen and paraffinic components are reacted in the presence of isomerization catalyst.In isomerization steps, pressure is generally 1 to 15MPa, and temperature is generally 200 to 400 ℃.Can use the VIII family metal that contains molecular sieve and period of element system, for example the special catalyst of Ni, Pt and Pd.Aluminum oxide and/or silicon-dioxide can be used as carrier.If if it is enough low with the product pour point to obtain branched structure by the chain extension reaction, isomerization does not need so.

Use aforesaid method mainly to comprise stable hydrocarbon and composition thereof by the product of biological starting material production.They can depend on the desired properties of base oil as base oil and the component that is used for production basis oil.The II+ group of API, the high quality base oil or the base oil component of preferred III group obtain the oil that described base oil or base oil component are particularly suitable for producing high quality lubricant, white oil, process oil and are used for metal working fluid as product.

Advantage of the present invention

Compare with the hydrocarbon ils that the corresponding viscosity of routine is classified, base oil of the present invention or base oil component have good processing performance.Narrow boiling spread represents that product does not contain any initial light ends (the expression molecule significantly is lighter than mean value) that is reduced demonstration by the product volatility.This point makes the oil consumption in the practical application reduce and the discharge minimizing.Also can not get " tailing " formed by heavy component (expression molecule overweight mean value significantly).This point causes the low temperature performance excellent of product.

For base oil of the present invention or base oil component, can carbon number and boiling spread be adjusted to required scope by selecting feedstock composition.For the base oil of prior art,, adjust boiling spread by the fraction that product of distillation obtains having required kinematic viscosity.Preferably lubricant comprises having the narrow carbon number range and the base oil of narrow boiling spread thus.In this way, contain base oil performance in a similar manner under different condition of the molecule of similar size.

Base oil of the present invention or base oil component mainly are made up of the isomerization paraffinic hydrocarbons, and all the other are monocycle alkane and more are being the bicyclic alkane of non-condensed on the low degree.As everyone knows, mononaphthene hydrocarbon compound and non-condensed bicyclic alkane have and the similar physicals of isoparaffin.Fused rings alkane in the prior art product has lower VI and relatively poor temperature-viscosity performance, and relatively poor oxidative stability.

For base oil of the present invention or base oil component, the high VI of product represents can reduce in practice the amount of the viscosity index improver VII that is generally used for lubricating oil composition.For example in engine oil, be known that usually the VII component is the sedimental major cause in the engine.In addition, the amount of VII reduces the remarkable saving that causes the formulation cost.

Opposite with conventional product derived from crude oil, do not have sulphur, nitrogen in base oil of the present invention or the base oil component, do not have aromatic substance yet, make its therein the user be exposed to oil or mist of oil this type of use in Secure Application.In addition, therefore product of the present invention can prolong the time limit of service by the lubricant of described base oil preparation, and expand its application at a lower temperature for the response excellence of oxidation inhibitor and pour point reducer (PPD).

With ester or contain heteroatomic other base oil and compare, with regard to hydrolysis, base oil of the present invention or base oil component are more stable, also are that it is not easy to decompose under wet condition and discharges corrosive acid.Base oil of the present invention is chemically also more stable than more reactive ester base oil, and in addition, compares with the ester base oil derived from the unsaturated fatty acids of biogenetic derivation, and its oxidation-resistance improves.

Compare with ester, nonpolar basic oil of the present invention or base oil component are more compatible with the base oil component and the lubricant additive that obtain derived from the conventional alkyl oil ingredient of crude oil, by the Fischer-Tropsch method.In addition, for the elastomerics of for example sealing material, this type of problem that does not have ester and run into.

The advantage of base oil of the present invention or base oil component comprises that it satisfies the II+ group according to API, preferred III group is for the requirement of base oil, and can be according to identical base oil interchange standard, other base oil as the API classification is used for the automotive engine oil composition.

As from product ¹⁴The C isotopic content can be analyzed, and base oil of the present invention or base oil component are derived from renewable natural resources.

According to the present invention, the recyclable organism starting material constitute the brand-new raw material resources of high quality stable hydrocarbon basis oil or base oil component.By using renewable raw materials to replace Nonrenewable resources, also can reduce the influential carbon dioxide emissions of Greenhouse effect.

By following examples explanation the present invention, do not wish to limit its scope now.

Embodiment

In embodiment 1 to 5, by method, by containing the paraffinic hydrocarbons that the biological starting material production of oxygen has long-chain based on ketonization.This product is suitable as base oil or the base oil component that does not have the blend restriction well, and further, this product is also compatible with slip additive.In embodiment 6, the detection of the ratio of the base oil of biogenetic derivation in traditional mineral base oil is shown.Table 4 shows among the embodiment 1 to 5 that table 5 shows the performance of prior art product by the performance of the base oil component of biological raw material preparing.

Embodiment 1

Prepare the hydrocarbon component by the stearic acid fraction

The mixture of hydrolyzing plant oil (linseed oil, soybean, sunflower and rapeseed oil), and obtain the product fraction according to the carbon number distilled fatty acid.As two keys quilts of the lipid acid fraction of raw material pre-hydrogenation selectively.Use the stearic acid fraction (C that obtains thus based on the raw-material paraffinic hydrocarbons diesel fuel dilution of biology ₁₇H ₃₅COOH).The stearic acid content of mixture is 31wt%.Use MnO ₂Catalyzer is this raw material of ketonization in continuous tubular reactor.The temperature of reactor is 370 ℃, and WHSV is 3.Obtain the 18-pentatriacontanone in the thinner, promptly stearone is as product.

In step of hydrogenation, use exsiccant and activatory NiMo/Al ₂O ₃Catalyzer, described stearone/diluent mixture that hydrogenation obtains in high pressure P arr reactor obtains straight-chain paraffin.Ketone hydrogenation under 330 ℃, the pressure of 5MPa, up to do not have the ketone peak in the IR of sample spectrum, mixing rate is 300rpm.Stearic acid produces linear C35 paraffinic hydrocarbons.

By straight-chain paraffin wax isomerization in the Parr reactor that ketone obtains, obtain the branched paraffin of base oil classification, use reductive Pt molecular sieve/Al ₂O ₃As catalyzer.Paraffinic hydrocarbons/the diluent mixture of the preheating that more than obtains is in 3MPa hydrogen pressure and 340 ℃ of following isomerization, up to the PP that obtains-6 ℃.At last, under vacuum, distillate light ends, by filtration over celite paraffin product is made with extra care subsequently.

Embodiment 2

By preparing the hydrocarbon component derived from palmitic lipid acid

Hydrolysis plam oil, and two keys of hydrogenation selectively.After the hydrogenation, lipid acid is composed as follows: C14 1%, and C16 44%, C18 54% and C20 1%, all percentages.As ketonization lipid acid among the embodiment 1, remove solvent by distillation after the ketonization.

In step of hydrogenation, use exsiccant and activatory NiMo/Al ₂O ₃Catalyzer, the alcohol/ketone mixtures that obtains more than the hydrogenation in the Parr reactor obtains straight-chain paraffin.Hydrogenation alcohol/ketone mixtures under the pressure of 3.3MPa, 340 ℃, 300rmp mixing rate.Plam oil produces straight-chain paraffin.

In the Parr reactor, the normal paraffin chloroflo that isomerization is obtained by hydrogenation by alcohol/ketone mixtures under 340 ℃, 3MPa hydrogen pressure produces the branched paraffin of base oil viscosity classification, uses reductive Pt molecular sieve/Al ₂O ₃Catalyzer is lower than-15 ℃ up to the PP point.At last, under reduced pressure distillate light ends.

Embodiment 3

Prepare the hydrocarbon component by fatty acid methyl ester

Under alkaline condition, 70 ℃, the pressure of 0.1MPa, in two steps, make the Tallow, beef of purification carry out transesterification with methyl alcohol, obtain fatty acid methyl ester thus.Sodium methylate is as catalyzer.By using acid and water washing purified reaction mixture.At last, the mixture of drying fatty acid methyl esters.

Mixture with the paraffinic hydrocarbons diesel fuel dilution fatty acid methyl ester of biogenetic derivation.The fatty acid methyl ester of the raw material that obtains is 30wt%, and among this raw material such as the embodiment 1 disclosed in continuous tubular reactor ketonization.Obtain saturated and beta-unsaturated ketone thus as product.

In step of hydrogenation, the alcohol/ketone mixtures that in the Parr reactor, obtains more than the hydrogenation as embodiment 2.Carry out isomerization as embodiment 2 equally.

Embodiment 4

Prepare the hydrocarbon component by Yatall MA based on isomerization lipid acid

In the Parr reactor, use the fatty acid mixt of mordenite catalyst isomerization from the distillation Yatall MA.H mordenite zeolite is as catalyzer, and water uses with the amount of the 3wt% of reaction mixture total mass.With this mixture of nitrogen purging.Isomerisation temperature is 280 ℃, and it is that 2.0MPa and mixing rate are 300rpm that nitrogen is pressed.Filter catalyzer, under reduced pressure distill monomer acids subsequently from product.

Use Pd/C catalyzer two keys of hydrogenation monomer acids selectively in the Parr reactor.Hydrogenation is carried out under the 1.8MPa hydrogen pressure at 150 ℃.By adding the hexane of doubling dose, subsequently mixture is cooled to-15 ℃, and filters the crystal of formation, remove linear fatty acid by mixture.At last, distillate solvent by the Unimac 5680 fraction.

Ratio with 30 to 70wt% is with the paraffinic hydrocarbons diesel fuel dilution Unimac 5680 fraction of biogenetic derivation.Use MnO ₂Catalyzer is this raw material of ketonization in continuous tubular reactor.The temperature of reactor is 370 ℃, and WHSV is 1.7.The mixture that obtains isomerization ketone thus is as product.

In step of hydrogenation, as embodiment 2 alcohol/ketone mixtures that hydrogenation obtains thus in the Parr reactor.Under reduced pressure distillate solvent by final product., by solvent dewaxing process from product extract n-paraffin thereafter, and last, by filtration over celite paraffin product is made with extra care.Mainly obtain branched paraffin as final product.

Embodiment 5

Prepare the hydrocarbon component by Yatall MA base isomerization lipid acid and dicarboxylic acid

With the Unimac 5680 fraction of 1: 3 molar ratio mixing according to dicarboxylic acid (hexanodioic acid) preparation of embodiment 4 and C6.Use MgO catalyzer this raw mix of ketonization in the Parr reactor.Mixing acid uses the mixing rate of 300rpm 340 ℃ of following ketonization.

In step of hydrogenation,, and under reduced pressure distillate light ends by final product as embodiment 1 alcohol/ketone mixtures that hydrogenation obtains in the Parr reactor.As product, obtain comparing the longer branched paraffin of chain with other embodiment.

The general introduction of embodiment 1-5

As carrying out among the embodiment 1-5, base oil component also can or reclaim food fats and oil (for example fried oil) by other plant, fish, animal, or derived from the ester or the soap of the lipid acid of described fat and oil, or corresponding pure and mild free fatty acids.The hydrocarbon component also can be by natural wax by carrying out processing in a similar manner, and described natural wax is made of lipid acid and alcohol.On the other hand, corresponding alcohol for example can use that the Ru/C catalyzer is prepared by lipid acid, and described alcohol can carry out traditional esterification with lipid acid.The ester that obtains carbon number C36 thus is used for ketonization, and natural wax is generally the C38-C46 ester simultaneously.

Embodiment 6

By C16 alcohol preparation hydrocarbon component derived from vegetables oil

Be condensation reaction, the C16 Fatty Alcohol(C12-C14 and C12-C18) of weighing 200g in the Parr reactor, the methoxylation sodium of Palladous chloride (5ppm palladium) and 12g.Mixing is adjusted to 250rpm, and temperature regulation to 250 ℃ and pressure are adjusted to 0.5MPa.Keep a spot of nitrogen purging, with the water that disengages in the cleaning reaction.React stable in GC analyzes up to the amount of condensed alcohols.After the reaction, use the hydrochloric acid neutralized reaction product, wash and use the calcium chloride drying with water.

In next HDO step, use exsiccant and activatory NiMo/Al ₂O ₃Catalyzer, the condensed alcohols that obtains more than the hydrogenation in high pressure P arr reactor obtains the methyl-branched paraffinic hydrocarbons.Hydrogenation deoxidation aldehyde under 340 ℃, the pressure of 5MPa, 300rpm mix is up to detecting less than pure peak in FTIR spectrum.The pour point of methyl-branched wax is 69 ℃.

Use reductive Pt molecular sieve/Al ₂O ₃Catalyzer, the C32 paraffin wax isomerization in the Parr reactor that more than obtains obtains the branched paraffin that base oil is classified.At the paraffinic hydrocarbons of 3MPa hydrogen pressure and 340 ℃ of following isomerization preheatings, up to the pour point that is lower than-15 ℃.At last, under reduced pressure by product distillation light ends.Provide the performance of condensation, hydrogenation deoxidation and hydroisomerizing base oil in the table 3.

Produce similar hydrocarbon compound by other condensation reaction and free radical reaction in a similar manner.

Table 4

The performance of the product of producing among the embodiment 1-6.

Analyze	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Method
Analyze	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6	Method	KV100(cSt)	5.2	4.3	5.8	65	16.4	4.3	ASTM D445
KV40(cSt)	23.0	18.3	27.7	34.0	150.5	18.2	ASTM D445	KV100(cSt)	5.2	4.3	5.8	65	16.4	4.3	ASTM D445
KV40(cSt)	23.0	18.3	27.7	34.0	150.5	18.2	ASTM D445	VI	164	153	159	148	115	145	ASTM D2270
Pour point (℃)	-6	-21	-18	-12	-12	-26	ASTM D5950	VI	164	153	159	148	115	145	ASTM D2270
Pour point (℃)	-6	-21	-18	-12	-12	-26	ASTM D5950	The GC distillation (℃)							ASTM D2887
10％	419	375		455		390		The GC distillation (℃)							ASTM D2887
10％	419	375		455		390		50％	475	457		481		444
90％	486	474		497		455		50％	475	457		481		444
90％	486	474		497		455		GC-Noack(w-％)	5.8	12.5		4.2		11.1	DIN 51581-2
Molecular distribution (w-%)								GC-Noack(w-％)	5.8	12.5		4.2		11.1	DIN 51581-2
Molecular distribution (w-%)								Aromatic hydrocarbons	0			0			ASTM D2549
Paraffinic hydrocarbons	88			31		90.4	FIMS	Aromatic hydrocarbons	0			0			ASTM D2549
Paraffinic hydrocarbons	88			31		90.4	FIMS	Monocycle alkane	12			49		9.2	FIMS
Bicyclic alkane	0			20		0.4	FIMS	Monocycle alkane	12			49		9.2	FIMS
Bicyclic alkane	0			20		0.4	FIMS	Other naphthenic hydrocarbon	0			0		0	FIMS
Sulphur, ppm	＜1			＜1			ASTM D3120/ D4294	Other naphthenic hydrocarbon	0			0		0	FIMS
Sulphur, ppm	＜1			＜1			ASTM D3120/ D4294	Nitrogen, ppm	＜1			＜1			ASTM D4629

Table 5

The performance of the base oil of prior art

Analyze	API GpIII， HC-CDW	API GpIII， HC-CDW	API GpIII， SW	API GpIV， PAO	Method
Analyze	API GpIII， HC-CDW	API GpIII， HC-CDW	API GpIII， SW	API GpIV， PAO	Method	KV100(cSt)	4.29	6.00	4.0	5.7	ASTM D445
KV40(cSt)	20.0	33.1	16.8	30	ASTM D445	KV100(cSt)	4.29	6.00	4.0	5.7	ASTM D445
KV40(cSt)	20.0	33.1	16.8	30	ASTM D445	VI	122	128	140	135	ASTM D2270
Pour point (℃)	-18	-12	-21	＜-63	ASTM D5950	VI	122	128	140	135	ASTM D2270
Pour point (℃)	-18	-12	-21	＜-63	ASTM D5950	CCS，-30℃(cP)	1750	4100		2300	ASTM D5293
CCS，-35℃(cP)	3100	7800	1560	3850	ASTM D5293	CCS，-30℃(cP)	1750	4100		2300	ASTM D5293
CCS，-35℃(cP)	3100	7800	1560	3850	ASTM D5293	The GC distillation (℃)					ASTM D2887
10％	395	412	394			The GC distillation (℃)					ASTM D2887
10％	395	412	394			50％	421	459	421
90％	456	513	459			50％	421	459	421
90％	456	513	459			GC-Noac k，w-％	13.3	5.8	12.5		DIN 51581-2
Molecular distribution, w-%						GC-Noac k，w-％	13.3	5.8	12.5		DIN 51581-2
Molecular distribution, w-%						Aromatic hydrocarbons	0,0	0,0	0,0	0,0	ASTM D2549
Paraffinic hydrocarbons	37,0	26,8	72,4	100	FIMS	Aromatic hydrocarbons	0,0	0,0	0,0	0,0	ASTM D2549
Paraffinic hydrocarbons	37,0	26,8	72,4	100	FIMS	Monocycle alkane	37,3	39,3	23,9	0	FIMS
Bicyclic alkane	16,1	20,3	3,5	0	FIMS	Monocycle alkane	37,3	39,3	23,9	0	FIMS
Bicyclic alkane	16,1	20,3	3,5	0	FIMS	Other naphthenic hydrocarbon	9,8	13,6	0,2	0	FIMS
Sulphur, ppm	＜0,2	＜0,2		＜1	ASTM D3120/ D 4294	Other naphthenic hydrocarbon	9,8	13,6	0,2	0	FIMS
Sulphur, ppm	＜0,2	＜0,2		＜1	ASTM D3120/ D 4294	Nitrogen, ppm	＜1	＜1		＜1	ASTM D4629

HC-CDW=hydrocracking, catalytic dewaxing base oil

Embodiment 7

By preparing the hydrocarbon component derived from palmitic lipid acid

Plam oil is hydrolyzed.Select the raw material of pre-hydrogenation as two keys of the following stated lipid acid derived from palmitic lipid acid.In independent evaporator unit, utilize nitrogen purging evaporation lipid acid, and use MnO ₂As catalyzer continuous ketonization in tubular reactor under atmospheric pressure.Temperature of reactor is 380 ℃, and the WHSV of raw material is 1l/h-1.

Use exsiccant and activatory NiMo/Al ₂O ₃Catalyzer, the C31 that the continuous hydrogenation deoxidation was obtained by the ketonization stage in tubular fixed bed reactor, C33, C35 alcohol/ketone mixtures.Under the WHSV of 4MPa (40 crust) pressure, 270 ℃ and 1l/h, carry out hydrogenation deoxidation.

Use reductive Pt molecular sieve/Al ₂O ₃Catalyzer, the straight-chain paraffin wax that obtains in the continuous isomerization HDO step in tubular fixed bed reactor uses reductive Pt molecular sieve/Al ₂O ₃Catalyzer obtains branched paraffin.Under 340 ℃, 4MPa hydrogen pressure, carry out isomerization, be lower than-15 ℃ up to the pour point of product.At last, under reduced pressure distill light ends and separation.

The hydrocarbon component also can be in a similar fashion produced by other plant and fish oil and animal tallow.

Table 6

The performance of product among the embodiment 7.

Method	Analyze	Base oil＞413 ℃	Base oil 356-413 ℃
Method	Analyze	Base oil＞413 ℃	Base oil 356-413 ℃	ASTM D 4052	Mi Du @15 ℃, kg/m ³	821.8	810.1
ASTM D 5950	Pour point, ℃	-23	-32	ASTM D 4052	Mi Du @15 ℃, kg/m ³	821.8	810.1
ASTM D 5950	Pour point, ℃	-23	-32	ASTM D 5771	Cloud point, ℃	-6.8	-24.7
				ASTM D 5771	Cloud point, ℃	-6.8	-24.7
				ASTM D 5293	CCS-30，mPas	1780
	CCS-35，mPas	2920	690	ASTM D 5293	CCS-30，mPas	1780
	CCS-35，mPas	2920	690
ASTM D 445	kV40，cSt	25.7	10.9
ASTM D 445	kV40，cSt	25.7	10.9	ASTM D 445	kV100，cSt	5.4	2.9
ASTM D 2270	VI	153	126	ASTM D 445	kV100，cSt	5.4	2.9
ASTM D 2270	VI	153	126
ASTM D 2887	10％，℃	431	355
ASTM D 2887	10％，℃	431	355		50％，℃	453	384
	90％，℃	497	415		50％，℃	453	384
	90％，℃	497	415	DIN 51581-2	GC Noack	4.4	33.1
				DIN 51581-2	GC Noack	4.4	33.1
				FIMS	Paraffinic hydrocarbons	90.5
	Monocycle alkane	9.5		FIMS	Paraffinic hydrocarbons	90.5
	Monocycle alkane	9.5			Bicyclic alkane	0
	Other naphthenic hydrocarbon	0			Bicyclic alkane	0
	Other naphthenic hydrocarbon	0
ASTM D 3120	S，mg/kg	0	0
ASTM D 3120	S，mg/kg	0	0	ASTM D 4629	N，mg/kg	0	0

Embodiment 8

The measurement of the hydrocarbon component of biogenetic derivation

The hydrocarbon component weighing of biogenetic derivation is entered mineral oil based III group base oil, and thoroughly mix.For first sample, the hydrocarbon component of the biogenetic derivation of weighing 0.5014g, and add the base oil component of III group with the amount that obtains the 10.0000g gross weight; For second sample, the hydrocarbon component of the biogenetic derivation of weighing 1.0137g, and add the base oil component of III group with the amount of 10.0232g gross weight.The result who measures sums up in following table 6.The content of radiocarbon C14 is expressed as " contemporary carbon % ", based on the radiocarbon C14 content in the nineteen fifty atmosphere.At present, the radiocarbon C14 content in the atmosphere is about 107%.δ ¹³C value representation stable carbon isotope ¹³C/ ¹²The ratio of C.By this value, the isotopic fractionation that obtains in our method can be corrected.An actual result in the end hurdle provides.

Table 7

Radiocarbon C14 content

Sample	¹⁴C content, %	δ ¹³C	Biological ratio, %
Sample	¹⁴C content, %	δ ¹³C	Biological ratio, %	Mineral oil	0.1±0.07	-29.4	0
Bio oil	106.7±0.4	-28.9	100	Mineral oil	0.1±0.07	-29.4	0
Bio oil	106.7±0.4	-28.9	100	Mineral oil+biology, 5wt%	5.0±0.3	-29.3	4.60±0.28
Mineral oil+biology, 10wt%	10.8±0.3	-26.9	10.04±0.29	Mineral oil+biology, 5wt%	5.0±0.3	-29.3	4.60±0.28

Embodiment 9

Carbon number distribution

The ratio of the narrow carbon number distribution of base oil product depends on distillation.The carbon number distribution of VHVI shown in Fig. 1 (413-520 ℃ of interruption) and base oil of the present invention (360-℃ of interruption).According to the present invention, when＞413 ℃ in a similar manner in during engler distillation, the carbon number distribution of base oil is narrower than the carbon number distribution of conventional base oil, is equivalent to the C26 paraffinic hydrocarbons.Compare with the conventional product of identical viscosities scope (KV100 is about 4cSt), base oil of the present invention contains more substantial heavy cut, as Fig. 1 for shown in the carbon number distribution.Carbon number＜the C31 of low boiling component is because the cracking in the isomerization.Higher-boiling compound improves VI.

Claims

1. base oil is characterised in that this base oil comprises that carbon number is the branched-chain saturated hydrocarbon of C18 at least, total carbon content in the base oil ¹⁴The C isotopic content is in nineteen fifty ¹⁴At least 50% of C isotropic substance level, its contain 90wt% at least stable hydrocarbon, be less than 10wt% straight-chain paraffin, be no more than 0.1% condensed polycyoalkane, and the carbon number range of the stable hydrocarbon of 50wt% is no more than 9 carbon at least.

2. according to the base oil of claim 1, be characterised in that ¹⁴The C isotopic content is preferably greater than 99% greater than 90%.

3. according to the base oil of claim 1 or 2, be characterised in that the carbon number range of the stable hydrocarbon of 75wt% is no more than 9 carbon at least.

4. according to each base oil of claim 1-3, be characterised in that its carbon number range width is 7 carbon at the most, preferably 5 carbon and especially preferably 3 carbon at the most at the most.

5. according to each base oil of claim 1-4, be characterised in that it comprises 95wt% at least, preferably 97wt% and the preferably stable hydrocarbon of 99wt% at least at least.

6. according to each base oil of claim 1-5, be characterised in that it comprises the straight-chain paraffin that is less than 5wt% and preferably is less than 1wt%.

7. according to each base oil of claim 1-6, be characterised in that it comprises 5-50% and preferred 5-30% and the especially preferred monocycle alkane of 5-15%.

8. according to each base oil of claim 1-7, be characterised in that it satisfies the group II+ according to API, the classification of preferred group III is for the requirement of base oil.

9. according to each base oil of claim 1-8, the CCS-30 viscosity that is characterised in that described base oil is at the most 29.797 ^*(KV100) ^2.7848CP, preferably at the most 34.066 ^*(KV100) ^2.3967CP; CCS-35 viscosity is at the most 36.108 ^*(KV100) ^3.069CP, preferably at the most 50.501 ^*(KV100) ^2.4918CP; Pour point is no more than-9 ℃, preferably is no more than-12 ℃ and especially preferably be no more than-15 ℃.

10. according to each base oil of claim 1-9, be characterised in that the viscosity index of described base oil is higher than 115, preferably be higher than 130, especially preferably be higher than 140 and preferably be higher than 150.

11., be characterised in that kinematic viscosity is that the basic oil volatility of 3cSt to 8cSt is not more than 2271.2 according to each base oil of claim 1-10 ^*(KV100) ^-3.5373%.

12., be characterised in that it is derived from the starting material that are selected from following biogenetic derivation according to each base oil of claim 1-11

I) described raw-material mixture.

13. according to each base oil of claim 1-12, be characterised in that it contains and be less than 10wt%, preferably be less than 5wt% and especially preferably be less than the aromatics carbon of 1wt%.

14., be characterised in that its sulphur content is less than 300ppm according to each base oil of claim 1-13, preferably be less than 50ppm, especially preferably be less than 10ppm and most preferably less than 1ppm.

15. according to each base oil of claim 1-14, be characterised in that its nitrogen content is less than 100ppm, preferably be less than 10ppm and especially preferably be less than 1ppm.

16. according to each base oil of claim 1-15, be characterised in that the boiling range of described base oil is 150 ℃ at the most, preferably at the most 100 ℃, especially preferably 70 ℃ and preferably 50 ℃ (heat up in a steamer and a little to be D10 and D90) at the most at the most.