CN101490222B - Combined lubricant and fuel package for use in an internal combustion engine - Google Patents

Abstract

The present invention relates to a combined lubricant and fuel composition package for operating a diesel engine, wherein the lubricant comprises a base oil comprising (i) a continuous series of iso-paraffins having n, n+1, n+2, n+3 and n+4 carbon atoms, and/or (ii) a continuous series of iso-paraffins having n, n+2 and n+4 carbon atoms and not containing n+1, and n+3; wherein n is between 15 and40; and wherein the fuel composition comprises a paraffinic gas oil component having a paraffin content of greater than 80 wt% paraffins and a saturates content of greater than 98 wt%, and to its use in the reduction of nitrogen oxide in engine operation.

Description

The lubricant and the fuel package that are used for the combination of oil engine

Technical field

The present invention relates to the lubricant and the fuel that in the combustion machine, are used in combination.More specifically, the present invention relates to lubricant and fuel package for the internal combustion compression ignition engine.

Background technology

In the last few years, the purposes that is used for oil engine, the particularly compression ignition engine of transportation and other energy-producing device more and more widely.Compression ignition engine (it is called " diesel engine " after being to invent in 1892 the Rudolf Diesel of first compression ignition engine in addition) is used in the main type of engine of passenger vehicle, the heavy-duty applications in the global range because of its high-level efficiency in Europe and occupies critical positions in the stationary power generation.

Diesel engine is oil engine; More specifically, it is compression ignition engine, and wherein fuel/air mixture is lighted a fire owing to compression causes temperature to raise by being compressed to it, rather than for example lights a fire as the sparking plug that uses in the petrol motor by independent ignition source.

Popularizing gradually of diesel engine causes at engine emission, more specifically the government pressure at the particulate matter in waste gas and the exhaust gas stream increases.

Reported multiple for the strategy of controlling and reduce the particularly particulate emissions of diesel engine in the last few years.These comprise mineral oil derived fuel and/or the synthol that uses fuel dope, specific low sulfur content as the use of describing among the US-A-20050154240 for example.The document discloses the height isoparaffin base gas oil that obtains from the fischer-tropsch process for reducing the granular material discharged purposes of compression ignition engine.Other method comprises that preparation contains active compound for example as the low-sulfur lubricant compositions of disclosed acidylate nitrogenous compound among the WO-A-02/24842.The method of other reduction particle waste discharge concentrates on engine management, more specifically as for example disclosed injection and combustion processes among the US-A-6651614.The trend of improving engine management causes higher temperature of combustion substantially, and this increases oxynitride formation.It is harmful to the health of plant and animal that oxynitride (NOx) is proved to be, with be difficult to quilt by the fixed bed catalyst system and lentamente by conversion (as those disclosed among the US-A-6696389 for example), and/or may need other trouble and processing complexity (as disclosed among the EP-A-1010870 for example).

Therefore, need the further oxynitride that reduces in the diesel exhaust.

The applicant has made us unexpectedly finding can obviously reducing the content of nitrogen oxides of exhaust gas by using the combination of specific lubricant and fuel at present.

Summary of the invention

Therefore, the lubricant that the present invention relates to make up and fuel composition wrap in the purposes in the diesel engine, wherein said lubricant comprises base oil, base oil comprises (i) and has n, n+1, n+2, the serial isoparaffin of a n+ and n+4 carbon atom, and/or (ii) has a n, a n+2 and n+4 carbon atom and do not contain the serial isoparaffin of n+1 or n+3 carbon atom, wherein n is 15-40, comprise the paraffinic hydrocarbons gas oil component of 5-100wt% with wherein said fuel composition, this paraffinic hydrocarbons gas oil component has greater than the paraffinicity of 80wt% paraffinic hydrocarbons with greater than the saturates content of 98wt%.

Description of drawings:

Fig. 1 has provided 4 comparisons of large diesel engine between test period.

Embodiment

The present invention relates to for lubricated compression-ignition internal combustion engine be diesel engine, reciprocator, rotary engine (being also referred to as Wankel engine) and wherein burning be similar design intermittently engine lubricant and simultaneously for the synergistic combination of the fuel that moves this engine.

The applicant found to use contain Fisher-Tropsch derived base oil and/or poly-alpha olefins (PAO) derive the lubricant of base oil can be obviously with the combination that contains the fuel of aforesaid paraffinic hydrocarbons gas oil component and unexpectedly reduce the discharged nitrous oxides of diesel engine.

The diesel engine of bag of the present invention to be used is lubricated, and namely lubricant forms film to minimize the direct contact between them between the surface of the parts of relative movement.This composite lubricating film has reduced the overheated of friction, wearing and tearing and generation between the moving parts.Lubricant also as moving fluid from lubricated parts surface displace since parts relative to each other or the heat that produces of the friction of the motion of oily relatively film.Usually, diesel engine contains crankcase, cylinder head and cylinder.Lubricant is present in the crankcase usually, therein crankshaft handle, bearing and the bottom that piston is connected to the bar of crankshaft handle is coated with lubricant.The rapid movement of these parts cause lubricant to splash and the internal surface of lubricating piston-ring and cylinder between surface in contact.This lubricant film also as the sealing between piston ring and the cylinder wall so that the combustion space in the cylinder and the spatial isolation in the crankcase.

Though do not wish to be confined to any particular theory, it is believed that the collaborative concrete highly paraffinic fuel of existence of remaining lubricant film has reduced the temperature of piston and cylinder surfaces together, thereby reduced the formation of oxynitride.

Fuel composition according to combination of the present invention is applicable to compression ignition engine.Therefore, because being suitable as the fuel of compression ignition engine, boiling spread and other structure comprise one or more fuel elements.Usually, this engine uses piston head lubricated, and this is preferred, because lubricant has contribution to engine cool like this.In this engine, piston forms the foundry goods of the cylinder sidewall part with top portion and hollow usually, and wherein the top portion top portion is formed with horizontal hollow space, and wherein lubricant circulates to cool off top portion at hollow space.Lubricant is supplied to hollow space by splashing.

Fuel composition preferably has at least 40 cetane value, less than the flash-point of the sulphur content of 100ppm and at least 68 ℃ with contain aromatic hydrocarbons less than 10 quality % in addition.Fuel composition of the present invention may contain one or more fuel elements, and wherein preferred at least a is paraffinic hydrocarbons gas oil component.Fuel can advantageously contain the mixture of two or more Fisher-Tropsch derived gas oil and/or kerosene stock, chooses wantonly and mixes with non-Fisher-Tropsch derived gas oil and/or kerosene.Fuel composition can contain normally used additive in the fuel in addition.

In the context of the present invention, paraffinic hydrocarbons gas oil component is represented to contain greater than the 80wt% paraffinic hydrocarbons, more preferably greater than the 90wt% paraffinic hydrocarbons with even more preferably greater than the composition of 95wt% paraffinic hydrocarbons.The isomery of the paraffinic hydrocarbons that exists in the paraffinic hydrocarbons fuel is preferably greater than 0.3 with the ratio of positive structure, more preferably greater than 1, even more preferably greater than 3.Paraffinic hydrocarbons fuel can substantially only contain isoparaffin.

Paraffinic hydrocarbons gas oil component preferably contain serial isoparaffin with n, n+1, n+2, n+3 and n+4 carbon atom and wherein n be 8-25.

This paraffinic hydrocarbons gas oil preferably obtains from the fischer-tropsch building-up process, particularly boiling point those in gas oil and/or kerosene scope.Preferably, paraffinic hydrocarbons gas oil component is Fisher-Tropsch derived gas oil or its blend.

Fuel composition of the present invention contains the mixture of n-paraffin and isoparaffin, the amount of n-paraffin less than the amount of 99% and aromatic hydrocarbons of fuel composition weight less than 10% of gas oil weight of fuel.

Preferably, the mass ratio of the isoparaffin of paraffinic hydrocarbons gas oil component and n-paraffin increases to C18 with the paraffinic hydrocarbons carbon number from C8 usually and increases.

The preferred boiling point of the component of gas oil component in typical diesel oil fuel (" gas oil ") scope, namely about 150-400 ℃ or 170-370 ℃.Its 90%w/w recovered temperature suitably is 300-370 ℃.

The gas oil component of using in the fuel composition of the present invention preferably contains at least 80%w/w, more preferably 90%w/w, the paraffinic components of 95%w/w at least most preferably at least, preferred isoparaffin and linear paraffins in addition.The weight ratio of isoparaffin and n-paraffin is suitably greater than 0.3 and can as many as 12; Be suitably 2-6.

" Fisher-Tropsch derived " expression fuel element or base oil are that the sintetics of fischer-tropsch condensation course or derived by it obtains.Respective explanations term " non-Fisher-Tropsch derived " thus.Fischer-tropsch derived fuel also can be described as GTL (gas is to liquid) fuel.In the presence of the catalyzer that is fit to and usually at high temperature under (for example 125-300 ℃, preferred 175-250 ℃) and/or the high pressure (for example 5-100 bar, preferred 12-50 clings to), Fischer-Tropsch reaction changes into the more hydrocarbon of long-chain (normally paraffinic hydrocarbons) with carbon monoxide and hydrogen:

N (CO+2H ₂)=(-CH ₂-) n+nH ₂The O+ heat.

In case of necessity, the hydrogen of use and carbon monoxide can not be 2: 1.Carbon monoxide and hydrogen itself can be available from organic or inorganic, natural or synthetic source, normally available from Sweet natural gas or available from organic derived methane.

The actual value of this ratio can part by for the preparation of determining available from the gas oil of fischer-tropsch synthesis product or the hydroconversion process of fuel element.Preferably, Fisher-Tropsch derived gas oil fuel contains the isoparaffin of 50%w/w at least.Also can there be some loop chain alkane.

Preferably, the alkyl branches number of each paraffin molecules of Fisher-Tropsch derived gas oil is on average greater than 1.The above-mentioned of the present invention Fisher-Tropsch derived gas oil of this paper can directly obtain from Fischer-Tropsch reaction, or for example obtains indirectly by the fractionation fischer-tropsch synthesis product or from the fischer-tropsch synthesis product of hydrotreatment.Hydrotreatment can comprise that hydrocracking is to regulate boiling spread (referring to for example GB-B-2077289 and EP-A-0147873) and/or hydroisomerizing to improve cold flow character by the ratio that increases the side chain paraffinic hydrocarbons.EP-A-0583836 has described two step hydroprocessing process, wherein at first fischer-tropsch synthesis product is carried out hydrocracking with basic acquisition paraffinic hydrocarbons hydrocarbon fuel making under the condition of carrying out hydrocracking (this hydrogenation two keys and oxygen-containing component) under its condition that isomery or hydrocracking do not take place substantially and hydrocracking and isomery subsequently at least part of products obtained therefrom being taken place.Separable (for example by distillation) required gas oil fraction subsequently.

Described in for example US-A-4125566 and US-A-4478955, can use other for example polymerization of synthetic aftertreatment, alkylation, distillation, cracking-decarboxylation, dewaxing, isomery and hydroforming, so that the fischer-tropsch condensed products is carried out modification.Be used for the synthetic typical catalyst of paraffinic hydrocarbons hydrocarbon fischer-tropsch and comprise period of element Table VIII family metal, particularly ruthenium, iron, cobalt or nickel as catalytic active component.These catalyzer that are fit to have for example been described in EP-A-0583836 (the 3rd and 4 page).

An example of fischer-tropsch base process is " The Shell Middle DistillateSynthesis Process ", the SMDS (ShellMiddle Distillate Synthesis) that describes among people's (seing before) such as van der Burgt.This process (being also referred to as Shell " gas is to liquid " or " GTL " technology sometimes) is come production middle runnings range product by Sweet natural gas (mainly the being methane) synthetic gas of deriving being changed into heavy long chain hydrocarbon (paraffinic hydrocarbons) wax, making this heavy long chain hydrocarbon (paraffinic hydrocarbons) wax hydrocracking and fractionation to produce for example spendable gas oil in the diesel fuel composition of liquid transportation fuels subsequently.At Bintulu, Malaysia uses a kind of version of SMDS method at present, and it utilizes fixed-bed reactor with blend in the automobile fuel that carries out catalytic conversion step and its gas oil product and the commercially available acquisition of petroleum derivation gas oil.

Can for example buy from Shell company by the gas oil that the SMDS method makes.The other example of Fisher-Tropsch derived gas oil has been described in EP-A-0583836, EP-A-1101813, WO-A-97/14768, WO-A-97/14769, WO-A-00/20534, WO-A-00/20535, WO-A-00/11116, WO-A-00/11117, WO-A-01/83406, WO-A-01/83641, WO-A-01/83647, WO-A-01/83648 and US-A-6204426.

Utilize the fischer-tropsch process, fischer-tropsch derived fuel does not have or does not contain sulphur and the nitrogen of detection limit level basically.Containing these heteroatomic compounds tends to as the poisonous substance of Fischer-Tropsch catalyst and therefore removes from raw material of synthetic gas.In fuel composition of the present invention, this can bring the other beneficial effect of catalyst performance effect aspect.

In addition, the fischer-tropsch process of operation does not produce or produces hardly aromatic component usually.Suitably measure by ASTM D4629, the aromaticity content of fischer-tropsch derived fuel is generally and is lower than 1%w/w, preferably is lower than 0.5%w/w and more preferably less than 0.1%w/w.

Generally speaking, for example compare with petroleum derivation fuel, fischer-tropsch derived fuel contains low-level relatively polar compound, particularly polar surfactant.It is believed that this can help to improve anti-foam and fog removal performance.These polar compounds can comprise and for example contain oxygen, sulfur-bearing and nitrogenous compound.Low-level sulphur is indicating low-level oxygen and the nitrogenous compound of containing usually in the fischer-tropsch derived fuel, because they are all removed by identical treating processes.

As mentioned above, fuel of the present invention can comprise the mixture of two or more Fisher-Tropsch derived gas oil and kerosene stock.The preferred boiling point of the component of Fisher-Tropsch derived gas oil (or its major portion, for example its 95%w/w or bigger) in typical diesel oil fuel (" gas oil ") scope, namely about 150-400 ℃ or 170-370 ℃.The 90%w/w recovered temperature of gas oil component suitably is 300-370 ℃.

Preferably, the mass ratio of the isoparaffin of paraffinic hydrocarbons gas oil and n-paraffin usually with the paraffinic hydrocarbons carbon number from C8 increase to that C18 increases and wherein fuel contain less than the sulphur of 0.05%m/m with less than the aromatic hydrocarbons of 10 quality %.Preferably, the alkyl branches number of each paraffin molecules of gas oil is on average greater than 1.Preferably, fuel contains at least 50 quality % isoparaffins.

Usually, the density of paraffinic hydrocarbons gas oil under 15 ℃ is 0.76-0.79g/cm ³Cetane value (ASTM D613) is at least 65, is preferably greater than 70, is suitably 74-85; Kinematic viscosity under 40 ℃ (ASTM D445) is 2-4.5, preferred 2.5-4.0, more preferably 2.9-3.7 centistoke; And sulphur content (ASTM D2622) is 5ppmw or littler, preferred 2ppmw or littler.

Preferably, paraffinic hydrocarbons gas oil be to use less than 2.5, preferably less than 1.75, more preferably the hydrogen of 0.4-1.5/carbon monoxide than and the product that uses cobalt-containing catalyst to make by the condensation reaction of fischer-tropsch methane ideally.It can be from fischer-tropsch synthesis product (for example describing GB-B-2077289 and/or the EP-A-0147873) acquisition of hydrocracking, or is more preferably the product that those (referring to above-mentioned) of for example describing among EP-A-0583836 from two stage hydroconversion process obtain.Under latter event, the preferred feature of hydroconversion process can be as disclosed in the 4-6 page or leaf of EP-A-0583836 and embodiment.Fuel composition of the present invention can comprise the mixture of two or more Fisher-Tropsch derived gas oil.Compatibly, any other fuel element that exists in fischer-tropsch derived fuel and the composition will all be liquid form under envrionment conditions.

The present invention can be used for fuel composition wherein and is applicable to and/or is intended for use to pass through that fuel (particularly diesel oil fuel) composition drives or otherwise in any system of consume fuel (particularly diesel oil fuel) composition.Especially, it applicable to and/or be intended for use in oil engine or the external combustion engine (preferred oil engine), more especially as automobile fuel with in the oil engine especially for compression ignition type (diesel engine) type.

Fuel composition is low or super low sulfur fuel composition or sulfur free fuel composition on the whole preferably, for example contain at the most 500ppmw, preferably be not more than 350ppmw, most preferably be not more than 100 or 50ppmw or even 10ppmw or sulphur still less.

When fuel composition was the motor vehicle diesel fuel composition, it preferably met current suitable standard specifications, for example EN 590:99.Compatibly, its density under 15 ℃ is 0.82-0.845g/cm ³Final boiling point (ASTM D86) is 360 ℃ or littler; Cetane value (ASTM D613) is 51 or bigger; Kinematic viscosity under 40 ℃ (ASTM D445) is the 2-4.5 centistoke; Sulphur content (ASTM D2622) is 350ppmw or littler; And/or total aromaticity content (IP 391 (mod)) is less than 11.

Fuel composition of the present invention preferably contains the non-Fisher-Tropsch derived diesel base fuel less than 50%v/v, be more preferably less than 30%v/v, still be more preferably less than 25%v/v, less than 20%v/v, still be more preferably less than 15%v/v, not only be more preferably less than 10%v/v, still be more preferably less than 8%v/v but also still be more preferably less than 5%v/v and most preferably less than the non-fischer-tropsch derived fuel of 2%v/v.

Fuel composition also can comprise the Fisher-Tropsch derived kerosene stock of 30%v/v at the most.Except as otherwise noted, all concentration of citation all refers to the percentage ratio of total fuel composition.Usually the concentration of selecting Fisher-Tropsch derived gas oil with density, cetane value, calorific value and/or other relevant nature of guaranteeing whole fuel composition within the required range, for example within commercial standard or management regulation.

Unless outside fischer-tropsch derived fuel and the fischer-tropsch derived fuel component, the fuel composition that uses in the combination of lubricant of the present invention and fuel can contain other component.

Basic fuel itself can be (additive-free) of adding additive (containing additive) or not adding additive.If the interpolation additive, then it will contain one or more and be selected from additive as static inhibitor, pipeline flow improver, FLOW IMPROVERS (as ethylene or CALCIUM ACRYLATE/maleic anhydride copolymers), oiliness additive, antioxidant and wax anti-deposition agent.

Known and commercially available acquisition contains the diesel fuel additive of purification agent.These additives can be added into diesel oil fuel with the level that reduces, removes or slow down the engine deposits accumulation.Be applicable in the fuel dope that example with the purification agent of realizing the object of the invention comprises the succinic diamide of polyolefine substituted succinimide or polyamine, for example polyisobutenyl succinimide or polyisobutylene amine succinamides, aliphatic amine, Mannich base or amine and polyolefine (for example polyisobutene) maleic anhydride.For example among GB-A-960493, EP-A-0147240, EP-A-0482253, EP-A-0613938, EP-A-0557516 and the WO-A-98/42808 succinimide dispersant additives is being described.Particularly preferably be for example polyisobutenyl succinimide of polyolefine substituted succinimide.

Remove outside the purification agent, additive can contain other component.Example has lubricity improver; Demisting agent, for example alkoxylate novolac polymer; Defoamer (for example polyether-modified polysiloxane); Ignition improver (n-Hexadecane improving agent) (for example those disclosed in nitric acid 2-(ethyl hexyl) ester (EHN), nitric acid cyclohexyl ester, 2-tert-butyl peroxide and the 27th row-Di 3 hurdles, US-A-4208190 the 2nd hurdle the 21st row); Rust-preventive agent (the propane of tetrapropylene base succsinic acid-1 for example, 2-glycol half-ester, or the polyol ester of succinic acid derivative, wherein have at least one alpha-carbon atom of succinic acid derivative contain 20-500 carbon atom do not replace or replace for example polyisobutene-the get pentaerythritol diester of succsinic acid of aliphatic hydrocarbyl); Corrosion inhibitor; Perfume compound; Wear preventive additive; Antioxidant (for example phenols is as 2,6-, two-tert-butyl phenol, or phenylenediamine such as N, N '-two-sec-butyl-p-phenylenediamine); Metal passivator; And combustion improving agent.Special preferable additives comprises lubricity improver, particularly when fuel composition has low sulfur content (for example 500ppmw or littler).In the fuel composition that adds additive, the convenient concentration that exists of lubricity improver is less than 1000ppmw, preferred 50-1000ppmw, more preferably 100-1000ppmw.The commercially available acquisition lubricity improver that is fit to comprises ester-and acid-based additive.For example describe other lubricity improver in the following patent literature, particularly relating to their purposes in low sulfur content diesel oil fuel:

" the The Lubricity of DieselFuels " of-Danping Wei and H.A.Spikes, Wear, III (1986) 217-235;

-WO-A-95/33805-cold flow improving agent is to promote the oilness of low-sulfur fuel;

The ester of some carboxylic acids of-WO-A-94/17160-and alcohol, wherein acid contains 2-50 carbon atom and alcohol contains one or more carbon atoms, particularly XU 61518.10 and two-isodecyl adipic acid ester, as reducing the fuel dope that the diesel engine injected system is worn and torn;

Some phosphorodithioic acid diester-glycol of-US-A-5490864-are as the anti-wear lubricating additive of low sulphur diesel fuel; With

Some contain the Alkylaromatics of at least one carboxyl that is connected with their virtue nuclear-WO-A-98/01516-, so that the anti-wear lubricating effect particularly to be provided in low sulphur diesel fuel.

Also preferable additives contains defoamer, more preferably with rust-preventive agent and/or corrosion inhibitor and/or oiliness additive combination.

Except as otherwise noted, the preferred 10000ppmw at the most of (active substance) concentration of this other component respectively in adding the fuel composition of additive, more preferably 0.1-1000ppmw advantageously is 0.1-300ppmw, for example 0.1-150ppmw.

In the fuel composition arbitrarily (active substance) concentration of demisting agent be preferably 0.1-20ppmw, more preferably 1-15ppmw, still more preferably 1-10ppmw advantageously is 1-5ppmw.(active substance) concentration of any ignition improver that exists is preferably 2600ppmw or littler, and more preferably 2000ppmw or littler is 300-1500ppmw expediently.

In case of necessity, binder component as listed above can blend in multifunctional additive for lubricating oils, preferably is dispensed in the fuel to obtain composition of the present invention with the amount that thinner is mixed together and multifunctional additive for lubricating oils can be fit to that is fit to.

Under the situation of diesel fuel composition, for example additive will contain purification agent (optional with aforesaid other component) thinner compatible with diesel oil fuel usually, and described thinner can be to carry oil (for example mineral oil); Polyethers, can be end-blocking or end-blocking not; Non-polar solvent, for example toluene, dimethylbenzene, petroleum spirit and Shell company sell with trade mark " SHELLSOL " those; And/or polar solvent, for example ester and particularly alcohol, for example hexanol, 2-Ethylhexyl Alcohol, decyl alcohol, different tridecanol and alcohol mixture for example Shell company sell with trade mark " LINEVOL " those, particularly (it is C to LINEVOL 79 alcohol _7-9Primary alcohol mixture or C _12-14Alcohol mixture (commercially available acquisition).Compatibly, additive level is 0-10000ppmw and preferably is lower than 5000ppmw.

The lubricant of combination and the lubricant of fuel package contain at least a base oil, this base oil have greater than the paraffinicity of 80wt% paraffinic hydrocarbons and greater than the saturates content of 98wt% and contain have n, the continuous series isoparaffin of n+1, n+2, n+3 and n+4 carbon atom, or have the serial isoparaffin of n, n+2 and n+4 carbon atom and wherein n be 15-35.

The preferred Fisher-Tropsch derived base oil of base oil, its have greater than the paraffinicity of 80wt% paraffinic hydrocarbons, greater than the saturates content of 98wt% and contain have n, the continuous series isoparaffin of n+1, n+2, n+3 and n+4 carbon atom, wherein n is 15-40.Under the situation of Fisher-Tropsch derived base oil, base oil contain have n, the continuous series isoparaffin of n+1, n+2, n+3 and n+4 carbon atom.Can be by having content and the existence of the continuous series isoparaffin of n, n+1, n+2, a n+3 and n+4 carbon atom in field desorption/field ionization (FD/FI) commercial measurement base oil or the basic raw material (i).In this technology, at first by use high performance liquid chromatography (HPLC) method IP368/01 that oily sample is separated into polarity (aromatic hydrocarbons) mutually and nonpolar (saturates) mutually, wherein as use pentane replacement hexane as described in this method as mobile phase.Use Finnigan MAT90 spectrometer analysis saturates and the aromatic fraction that is equipped with field desorption/field ionization (FD/FI) interface subsequently, wherein use FI (" soft " ionization technique) to lack the kind of measuring hydrocarbon according to carbon number and hydrogen.In mass spectrograph, by formed characteristic ion compound is classified and classified by " z value " usually.This is by being used for the general formula C of all hydrocarbon species _nH _2n+zProvide.Because saturates separates analysis mutually with aromatic hydrocarbons, so can measure the content of the different isoparaffins with identical stoichiometry or n value.The use business software (gather 32, can be from Sierra AnalyticsLLC, 3453 Dragoo Park Drive, Modesto, California GA95350 USA obtains) mass spectrometric result is handled, to determine the relative proportion of all kinds of hydrocarbon.

Hydroisomerizing by paraffin wax, preferably carry out the dewaxing (for example solvent dewaxing or catalytic dewaxing) of some kinds subsequently, obtain aforesaid contain continuous series different-base oil of paraffinic hydrocarbons.Paraffin wax is Fisher-Tropsch derived wax.

In this manual the base oil that obtains from fischer-tropsch wax as described herein is called Fisher-Tropsch derived base oil.The example that for example can be used for preparing the fischer-tropsch process of above-mentioned Fisher-Tropsch derived base oil is the slurry attitude phase overhead product technology of the Sasol of so-called commerce, middle distillate synthetic method and " AGC-21 " Exxon Mobil method of Shell.These processes and other process have for example been described in EP-A-776959, EP-A-668342, US-A-4943672, US-A-5059299, WO-A-9934917 and WO-A-9920720 in more detail.Usually, these fischer-tropsch synthesis products comprise and contain 1-100 and even greater than the hydrocarbon of 100 carbon atoms.This hydrocarbon product will contain n-paraffin, isoparaffin, oxygenated products and unsaturated product.If base oil is a kind of required different-paraffin products, then it can advantageously use the Fischer-Tropsch derived feed of phase counterweight.In the Fischer-Tropsch derived feed of phase counterweight at least 30wt%, preferred 50wt% at least and more preferably at least the compound of 55wt% contain at least 30 carbon atoms.Contain at least 60 or the weight ratio of the compound of more carbon atoms and the compound that contains at least 30 carbon atoms preferably at least 0.2 in addition in the Fischer-Tropsch derived feed, more preferably at least 0.4 and most preferably at least 0.55.The C that preferred Fischer-Tropsch derived feed contains ₂₀₊The ASF-α value of cut (the Anderson-Schulz-Flory chainpropagation factor) is at least 0.925, preferably at least 0.935, more preferably at least 0.945, even more preferably at least 0.955.This Fischer-Tropsch derived feed can be by producing the phase counterweight as mentioned above the arbitrary process of fischer-tropsch products obtain.Not all fischer-tropsch process all produces this heavy product.The example of the fischer-tropsch process that is fit to has been described in WO-A-9934917.Fisher-Tropsch derived base oil will not contain or contain very a spot of sulfur-bearing and nitrogenous compound.For the product that obtains from the Fischer-Tropsch reaction of using synthetic gas free from foreign meter substantially, this is typical.Sulphur and nitrogen level are usually less than detection limit, are respectively to sulphur 5mg/kg with to nitrogen 1mg/kg at present.

This process will generally include that fischer-tropsch is synthetic, hydroisomerizing step and optional depression of pour point step, wherein said hydroisomerizing step and optional following the carrying out of depression of pour point step: (a) hydrocracking/hydroisomerizing fischer-tropsch products, (b) product separation with step (a) becomes at least a or multiple overhead product fuel fraction and base oil or base oil middle runnings.

If the viscosity of the base oil that obtains in the step (b) and pour point, then do not need other processing as required and described oil can be used as base oil of the present invention.In case of necessity, can carry out solvent dewaxing or preferred catalytic dewaxing to obtain to have the oil of preferred low pour point by the oil that obtains in to step (b) in step (c), compatibly further reduce the pour point of base oil middle runnings.Can obtain the required viscosity of base oil by going out the product of the suitable boiling spread of corresponding required viscosity from middle base oil fraction or from the oily fractionation by distillation of dewaxing.Compatibly, distillation can be the vacuum distilling step.

The reaction of the hydrocracking of step (a)/hydroisomerizing is preferably carried out in the presence of hydrogen and catalyzer, and this catalyzer can be selected from those of this reaction of being applicable to well known by persons skilled in the art, hereinafter will be described in more detail some this class catalyzer.In principle, catalyzer can be as known in the art any suitable in the catalyzer of isomerization paraffin molecules.Usually, hydrocracking/the hydroisomerization catalyst that is fit to is to contain those of the hydrogenation component of carrier band on refractory oxide carrier, and described carrier is the mixture of soft silica-aluminum oxide (ASA), aluminum oxide, fluorided alumina, molecular sieve (zeolite) or two or more these materials for example.A kind of preferred catalyzer that uses in hydrocracking of the present invention/hydroisomerizing step is that platiniferous and/or palladium are as the hydrocracking/hydroisomerization catalyst of hydrogenation component.Hydrocracking/hydroisomerization catalyst very preferably comprises platinum and the palladium of carrier band on soft silica-aluminum oxide (ASA) carrier.The amount of platinum and/or palladium is suitably 0.1-5.0wt%, is 0.2-2.0wt% more suitably, calculates and with the gross weight of carrier in element.If all exist, then the weight ratio of platinum and palladium can change in relative broad range, but is suitably 0.05-10, is 0.1-5 more suitably.The example of the precious metal that the ASA catalyzer is fit to is for example disclosed in WO-A-9410264 and EP-A-0582347.Other noble metal-based catalysts that is fit to, for example platinum on the fluorided alumina carrier are disclosed in for example US-A-5059299 and WO-A-9220759.Second kind of suitable hydrocracking/hydroisomerization catalyst is to contain at least a group vib (preferred tungsten and/or molybdenum) and at least a non-noble metal VIII family's metal (preferably nickel and/or cobalt) as those of hydrogenation component.These metals can exist with oxide compound, sulfide or their array configuration.The amount of group vib metal is suitably 1-35wt%, is 5-30wt% more suitably, calculates and with the gross weight of carrier in element.The amount of non-noble metal VIII family metal is suitably 1-25wt%, and preferred 2-15wt% calculates and with the gross weight of carrier in element.Found that particularly suitable such hydrogenation conversion catalyst is to contain the nickel of carrier band on fluorided alumina and the catalyzer of tungsten.

Above-mentioned non-noble metal-based catalysts preferably exists with their sulphided form.For keeping the catalyzer of sulphided form during use, need to exist some sulphur in the raw material.Preferably there are 10mg/kg and the more preferably sulphur of 50-150mg/kg at least in the raw material.

The preferred catalyzer that can the unsulfided form uses comprise carrier band on acid carrier with IB family metal for example non-noble metal VIII family metal for example iron, the nickel of copper coupling.Preferably exist copper to suppress that hydrogenolysis of paraffins is become methane.The pore volume of catalyzer preferably is determined as 0.35-1.10ml/g by water-absorbent, and surface-area is 200-500m by BET nitrogen determining adsorption preferably ²/ g and bulk density are 0.4-1.0g/ml.Support of the catalyst is preferably made by soft silica-aluminum oxide, and wherein the amount of aluminum oxide can be 5-96wt%, preferred 20-85wt%.As SiO ₂Dioxide-containing silica be preferably 15-80wt%.Carrier also can contain a small amount of for example tackiness agent of 20-30wt%, for example aluminum oxide, silicon-dioxide, IVA family metal oxide and multiple clay, magnesium oxide etc., preferably aluminum oxide or silicon-dioxide.At Ryland, Lloyd B., Tamele, M.W. and Wilson, J.N., Cracking Catalysts, Catalysis: volume VII, Ed.PaulH.Emmett, Reinhold Publishing Corporation, New York has described the preparation of soft silica-aluminum oxide micro-sphere body in 1960, the 5-9 pages or leaves.

By metal being flooded altogether to carrier, is carrying out drying under 100-150 ℃ and calcining under 200-550 ℃ in air from solution, the preparation catalyzer.VIII family metal amount is about 15wt% or littler, preferred 1-12wt%, and I B family metal exists with littler amount usually, and for example the weight ratio with VIII family metal is 1: about 1: 20 of 2-.

Provided typical catalyzer below:

Ni，wt％ 2.5-3.5

Cu，wt％ 0.25-0.35

Al ₂O ₃-SiO ₂wt％ 65-75

Al ₂O ₃(tackiness agent) wt% 25-30

Surface-area 290-325m ²/ g

Pore volume (Hg) 0.35-0.45ml/g

Bulk density 0.58-0.68g/ml

Hydrocracking/the hydroisomerization catalyst that is fit to of another kind be based on those of molecular sieve material, compatibly contains at least a VIII family metal component, preferably Pt and/or Pd be as hydrogenation component.Zeolite and other alumino-silicate materials of being fit to then comprise zeolite beta, zeolite Y, super steady Y, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-68, ZSM-35, SSZ-32, ferrierite, mordenite and silicon-dioxide-aluminophosphates for example SAPO-11 and SAPO-31.The example of the hydroisomerizing/hydroisomerization catalyst that is fit to has been described in WO-A-9201657 for example.Also can use the combination of these catalyzer.Fit closely hydrocracking/hydroisomerizing process is to comprise those of first step and second step, wherein uses zeolite beta or ZSM-48 is catalyst based and use ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-68, ZSM-35, SSZ-32, ferrierite or mordenite catalyst based in second step in first step.In back one group, preferred ZSM-23, ZSM-22 and ZSM-48.Described the example of this process in US-A-20040065581, it discloses the process that contains first step catalyzer (platiniferous and zeolite beta) and the second step catalyzer (platiniferous and ZSM-48).These processes can produce the base oil product that does not need other dewaxing step.

The combination of wherein using the aforesaid amorphous catalyst that contains silica-alumina carriers at first fischer-tropsch products to be carried out the first hydroisomerizing step and uses the catalyzer that contains molecular sieve to carry out the second hydroisomerizing step subsequently has been proved to be the preferred process for the preparation of the base oil that uses among the present invention.More preferably the first hydroisomerizing step and the second hydroisomerizing step are carried out with crossfire.Most preferably these two steps are carried out in the single reactor of the bed that contains above-mentioned amorphous and/or crystal catalyst.

In the step (a), in the presence of high temperature, high pressure, catalyzer, raw material is contacted with hydrogen.Temperature is generally 175-380 ℃, preferably is higher than 250 ℃ and more preferably 300-370 ℃.Pressure is generally 10-250 bar and preferred 20-80 bar.Can 100-10000Nl/l/hr, the gas hourly space velocity supply hydrogen of preferred 500-5000Nl/l/hr.Can 0.1-5kg/l/hr, preferably be higher than 0.5kg/l/hr and provide hydrocarbon feed more preferably less than the weight hourly space velocity of 2kg/l/hr.Hydrogen can be 100-5000Nl/kg and preferred 250-2500Nl/kg with the ratio of hydrocarbon feed.

Transformation efficiency in the step (a) be defined as at every turn by the time reaction generate the weight percentage that boiling point that boiling point is lower than 370 ℃ cut is higher than 370 ℃ raw material, this transformation efficiency is 20wt% at least, preferred 25wt% at least, but preferably be not more than 80wt%, more preferably no more than 65wt%.As above employed raw material is the total hydrocarbon feed that adds step (a) in the definition, and therefore the high boiling fraction that can obtain in the step (b) of arbitrarily optional recirculation is also arranged.

In step (b), preferably the product separation with step (a) becomes one or more overhead product fuel fraction and has base oil or the base oil precursor fraction of required viscometric properties.If pour point is not within the required range, then by dewaxing step (c), preferably further reduce the pour point of base oil by catalytic dewaxing.In this embodiment, the cut of the wideer boiling point of the product of step (a) is dewaxed to bring additional advantage.Can advantageously from the gained dewaxed product, separate base oil and the oil with required viscosity by distillation subsequently.Preferably as described in for example WO-A-02070629 dewax by catalytic dewaxing, the disclosure document is incorporated this paper by reference into.In case of necessity, to the final boiling point of the raw material of the step that dewaxes (c) can be the final boiling point of product of step (a) or lower.

Replacedly, although because its preparation process is expensive and preferred inadequately, but base oil preferably has greater than the paraffinicity of 80wt% paraffinic hydrocarbons with greater than the saturates content of 98wt%, with contain have n, the serial isoparaffin of n+2 and n+4 carbon atom (but not containing n+1 and n+3), wherein n is 15-40.Preferably, this base oil is hydrogenation poly-alpha olefins (PAO) homopolymer polymer, and namely alpha-olefin (PAO) base oil of deriving is classified as API IV group base oil usually.More preferably, the composition of PAO base oil comprises dimer, tripolymer, the tetramer, pentamer and six aggressiveness or their blend of alpha-olefin (for example 1-decene, 1-dodecylene).

Poly-alpha olefins (PAO) is to be suitable for the hydrocarbon blends of making synthetic base oil, makes by alpha-olefin or the oligomeric of 1-alkene.By make linear alpha-olefin oligomeric, carry out hydrogenation subsequently and constitute and make PAO to obtain desired product to remove unsaturated composition and fractionation.In the PAO preparation, 1-decene is the most frequently used alpha-olefin, but also can use the 1-octene, 1-dodecylene and tetradecene.Usually use the numerical value of the approximate viscosity (centistoke) of indication PAO under 100 ℃ that PAO is classified.Can use PAO 2, PAO 2.5, PAO 4, PAO 5, PAO 6, PAO 7, PAO 8, PAO 9, PAO 10 and their combination in the known engine oil.Viscosity is more high, and the mean chain length degree of poly-alpha olefins is more long.The isomeric distribution of used poly-alpha olefins depends on purposes.The typical poly-alpha olefins that makes from 1-decene mainly contains tripolymer (C30-hydrocarbon) and contains dimer, the tetramer, pentamer and six aggressiveness of much less.Though 1-decene is the most frequently used starting material, according to the required alpha-olefin that also can use other of product oil.PAO oil contains the isomer of larger amt, and (for example the tripolymer of 1-decene contains many C ₃₀Isomer, the tetramer contain many C ₄₀Isomer), this is derived from the skeleton branching (Shubkin 1993) during oligomeric.The most frequently used in these is PAO 4, PAO 6 and PAO 8.At Kirk-Othmer Encyclopedia ofChemical Technology, 3rd ed., 14,477-526; The lubricant formulations that contains these PAO base oils has been described among US-A-4218330 and the EP-A-1051466.

Independently, no matter be Fisher-Tropsch derived base oil or the PAO-base oil of deriving, the kinematic viscosity of base oil component under 100 ℃ is suitably and is 1-25mm ²/ second.Its kinematic viscosity under 100 ℃ is preferably 2-15mm ²/ second, more preferably 2.5-8.5mm ²/ second, 2.75-5.5mm more preferably still ²/ second.

Clearly, also can use the derive mixture of base oil of Fisher-Tropsch derived base oil and PAO-.

The pour point of base oil preferably is lower than-30 ℃.

Measure by ASTM D92, the flash-point of base oil is preferably greater than 120 ℃, more preferably even greater than 140 ℃.

The preferred 100-600 of the viscosity index of the lubricant that in bag of the present invention, uses, more preferably 110-200 and even more preferably 120-150.

The lubricant that in bag of the present invention, uses can only contain paraffinic base oil as base oil component contain the combination of aforesaid paraffinic base oil and ester or alternatively with other other base oil combination.Other base oil compatibly account for total fluid recipes less than 20wt%, be more preferably less than 10wt%, also be more preferably less than 5wt%.The example of these base oils is mineral based paraffinic and naphthenic base oils and synthetic base oil, for example poly-alpha olefins, polyalkylene glycol and analogue.Institute's consumption reduces restriction by the oxynitride that expectation obtains.Preferably, in total lubricant, lubricant comprises the saturated cyclic hydrocarbons of 5-10wt% in addition, because this has improved the low temperature compatibility of different components in the lubricant.

Lubricant of the present invention preferably contains the viscosity modifier of 0.01-30wt% in addition.Viscosity index improver (also being known as VI improving agent, viscosity modifier or viscosity modifier) provides high temperature and low temperature operability to lubricant.These additives provide acceptable at low temperatures viscosity and shear stable preferably.The lubricant that uses in bag of the present invention preferably contains other other lubricant composition of at least a significant quantity in addition, for example polarity and/or nonpolar lubricant base oil and performance additive are such as but not limited to metal and ashless oxidation retarder, ashless dispersant, metal and ashless detergent, corrosion inhibitor and rust-preventive agent, metal passivator, metal and nonmetal, low ash, phosphorous and non-phosphorus, sulfur-bearing and the non-S antiwear additive that contains, metal and nonmetal, phosphorous and non-phosphorus, sulfur-bearing and non-sulfur-bearing extreme-pressure additive, antitack agent, pour point depressant, the wax conditioning agent, viscosity modifier, the sealing compatilizer, friction modifier, the oilness agent, the anti-coloring agent, chromogenic reagent, defoamer, emulsion splitter and other additive-package of often using.For the summary of the additive of multiple frequent use, with reference to the Lubricants and RelatedProducts of D.Klamann, Verlag Chemie, Deerfield Beach, FL; " the Lubricant Additives " of ISBN 0-89573-177-0 and M.W.Ranney, by Noyes DataCorporation of Parkridge, N.J. publishes (1973).

The present invention relates to the engine configurations for generation of kinetic energy and heat energy in addition, comprise lubricated diesel engine and fuel distribution and stocking system, wherein said diesel lubrication agent contains: (i) Fisher-Tropsch derived base oil or oil base stock, described Fisher-Tropsch derived base oil or oil base stock have greater than the paraffinicity of 80wt% paraffinic hydrocarbons and greater than the saturates content of 98wt% and contain have n, the continuous series isoparaffin of n+1, n+2, n+3 and n+4 carbon atom and wherein n be 15-40; And/or (ii) base oil or oil base stock, described base oil or oil base stock have greater than the paraffinicity of 80wt% paraffinic hydrocarbons and greater than the saturates content of 98wt% and contain have n, n+2 and n+4 carbon atom but do not contain n+1 and the serial isoparaffin of n+3 carbon atom, wherein n is 15-40; Wherein fuel distribution and stocking system contain fischer-tropsch derived fuel.

The advantage of this configuration is that fuel and lubricant all more can be by biological degradation than suitable mineral oil based lubricant and/or fuel.In addition, the high oxidation stability of this fuel and lubricant can allow not operate for a long time and not influence the quality of fuel and lubricant and therefore reduce oxidation products and for example the organic acid that fuel distribution and stocking system and engine produce corrosion is formed.Engine can be for example rotary pump, in-line pump, modular pump, electronic unit syringe or joint-track type of direct injection, or pouring-in indirectly.It can be heavy type or LD-diesel.

With use fischer-tropsch or PAO derive lubricant the diesel oil fuel operation of mineral oil basis or use the mineral oil based lubricant to compare with Fisher-Tropsch derived diesel-fuel operation, produce oxynitride still less during this engine configurations operation.This engine configurations is preferably formed the part of carrier vehicle or stationary installation.More preferably conveyer is for example truck or locomotive or light-duty conveyer passenger vehicle for example of heavy conveyer.Replacedly, it can form for example part of water pump of stationary installation, and wherein its other advantage is that can to prepare that lubricant and fuel make when taking place to pollute because of Fisher-Tropsch derived gas oil and the intrinsic high biological degradability of base oil be nontoxic or almost non-toxic to marine organisms.Again replacedly, it can form for example part of power set (for example emergent or auxiliary generator) of stationary installation, wherein compares with the mineral oil based Equivalent, and the base oil of high oxidation stability and the existence of fuel will prolong inactive time.

The present invention relates to the method for generating electricity in addition under the condition that reduces exhaust gas emission, comprise and use the operating fuel diesel engine that contains Fisher-Tropsch derived gas oil, wherein with the lubricated described diesel engine of the lubricant compositions that contains base oil or oil base stock, described base oil or oil base stock have greater than the paraffinicity of 80wt% paraffinic hydrocarbons with greater than the saturates content of 98wt% with contain (i) and have n, n+1, n+2, the continuous series isoparaffin of a n+3 and n+4 carbon atom and wherein n be 15-40, and/or (ii) has a n, the serial isoparaffin of a n+2 and n+4 carbon atom (but not containing n+1 and n+3 carbon atom), wherein n is 15-40.

The present invention will further specify by following non-limiting examples:

Embodiment 1

Fuel composition

Prepare two kinds of automobile gas oil compositions: fischer-tropsch automobile gas oil (F-T AGO) blend is made of R655 lubricity improver and STADIS 450 anti static additives of basic fuel (S040990) with 250mg/kg.Conventional automobile gas oil (mineral AGO) is the 50ppm sulphur fuel that satisfies European EN590 standard.The fuel code is DK1703.The composition of two kinds of fuel has been described in the table 1:

Table 1

Fuel performance	Testing method	F1	Contrast F2
				15 ℃ of (g/cm of density 3) distillation IBP (℃) 10% 20% 30% 40% 50% 60% 70% 80% 90% 95% 40 ℃ of (centistoke) (mm of FBP cetane value kinematic viscosity 2/ s) cloud point (℃) sulphur (WDXRF) (ppmw)	IP 365/ ASTM D4052 IP 123/ ASTM D86 ASTM D613 IP 71/ ASTM D445 DIN EN 23015 ASTM D2622	0.7846 219.5 245.9 258.8 270.1 282.5 295.2 307.2 317.7 328.1 342.1 353 358.2 79 3.497 -0.5 ＜5	0.8326 169.0 209.0 231.0 249.0 262.5 274.5 285.5 296.5 309.0 327.0 342.0 357.0 54.8 2,895 -11 49

[0099]Gas oil fuel F1 through with EP-A-0583836 in the similar two stage hydroconversion process described obtain from fischer-tropsch (SMDS) sintetics.Contrast fuel is conventional mineral oil derived low-sulfur automobile gas oil.

Lubricant

Prepare two kinds of lubricant formulations.For the purpose of this test, the base oil that uses in the lubricant compositions is API Gp III base oil:

First base oil (BO1) is (100%) Fisher-Tropsch derived base oil completely, and it uses, and (Bintulu, Malaysia) the fischer-tropsch waxy raffinate of Huo Deing is as raw material from ShellSMDS Bintulu.This raw material had carried out the solvent dewaxing step and the kinematic viscosity under 100 ℃ is 5.0cSt.Use that YuBase Gp III constitutes the two kinds blends (BO2) available from the mineral derived base oil of hydrogenation wax stock (also be known as fuels hydrocracker tower at the bottom of oil) are to be used for contrast, specifically be YuBase 4 (BO2 component 1) and YuBase 6 (BO2 component 2), the two all can be from SK BaseOils, Ulsan, Korea is commercially available.The kinematic viscosity of blend under 100 ℃ is 5.0cSt.

With commercially available additive-package BO1 and BO2 are formulated in the lubricant.Prescription is based on grey heavy-duty diesel oil among the present commercial 5W-40 API-CH4, referring to table 2.

About Vk100C and the cold crank viscosity (VdCCS) under-30 ℃, fischer-tropsch base oil blend and YuBase blend are comparable.The Noack volatility of fischer-tropsch base oil is lower slightly, even its kinematic viscosity (VK100 ℃) and its VdCCS under 100 ℃ is lower than the YuBase analogue reluctantly.

Table 2 5W-40 lubricant feature

Component		LB1	Contrast LB
				BO1 (fischer-tropsch)		74.41	-
BO2 component 1		-	63
				BO2 component 2		-	11
Additive-package 1		13.0	13.0
				Additive-package 2		0.6	0.6
Pour point depressant		0.2	0.2
				Antioxidant		0.5	0.5
Viscosity modifier		11.29	11.7
				Kinematic viscosity under 100 ℃ [cSt]		14.46	14.27
CCS[pool under-30 ℃]		65.17	61.23

[0107]Lubricant above using and fuel composition be lubricated and operation automobile heavy duty engine (table 3) respectively:

Table 3-engine standard and rated performance data

Model:	MAN TG-A410A
		Engine:	MAN D2866 LF28 six cylinder DI diesel engine have exhaust gas recirculation (EGR)
Cylinder:	Six polyphones
		Cylinder diameter/stroke:	128×155mm
Volume:	11.97 rise
		Peak power:	403hp(301kW)，1,900rpm
Peak torque:	1,850Nm(1,363lbft)，900-1,300rpm
		Variator:	ZF 16-directly drives at a high speed, has the selection of ratio of gear section, splitter and MAN Comfort Shift

Measure discharged nitrous oxides.

The discharged nitrous oxides data of MAN Euro 3 heavy duty engines

It other 85 hours was after total run time is 100 hours that Fig. 1 has provided in pre-chlorisis (degreening) lubricant oils 15 hours and operation engine, the simple comparison of the NOx discharging that records.(chlorisis is the method for stable lubricants, and wherein the wear-resistant component of additive is partly decomposed and is distributed on the metallic surface and the most volatile light ends evaporation of base oil).Preference pattern 13 Europe fixed cycle (ESC) are as the basis of mileage accumulation and emission test.In this test, under the power output that equates, on the engine power meter, through a series of equilibrium modes engine is tested.Under each pattern, the operation engine is finished engine speed and load variations through predetermined time in 20 initial seconds.The speed of regulation is remained on ± 50rpm in and make the moment of torsion of regulation remain on peak torque under the test speed ± 2% in.During each pattern, measure discharging and use one group of weighting factor that the described cycle is averaged.Under 13 patterns, on a strainer, particulate emissions is sampled.Final emission result is represented with g/kW h.

As can be seen from Figure 1, for stable lubricant formulations, when using paraffinic hydrocarbons (Fisher-Tropsch derived) gas oil to act as a fuel and using mineral low-sulfur diesel gas oil to act as a fuel to reduce the NOx discharging when comparing.For paraffinic lubricant prescription of the present invention and contrast mineral derived Gp III base oil class prescription, the result is not always the case.

Make us unexpectedly finding, for through stable lubricant after engine working time of 100 hours altogether, when the engine power unit of being output as with gram/kilowatt-hour (g/kW h) carries out simple and absolute comparison to NOx discharging, compare the NOx discharging that the fischer-tropsch base lubricating agent is obviously reduced with mineral Gp III base oil base lubricating agent.As shown in table 4, under with the prerequisite that for example influence of fuel consumption poor (as monitoring by Carbon emission) is taken into account, compare with the combination of paraffinic hydrocarbons, Fisher-Tropsch derived automobile gas oil with combination or the mineral derived base oil in the lubricant of mineral oil derived fuel with the paraffinic base oil in the lubricant, in the lubricant combination results of paraffinic base oil of the present invention and paraffinic hydrocarbons fuel of the present invention the discharged nitrous oxides of beyond thought collaborative nonlinear formation per unit carbonic acid gas significantly reduce.

The NOx reduction value of table 4-after relevant fuel consumption is taken into account

Experiment	The effect of measuring	Δ NOx discharges [g/kW h]	Δ NOx be benefited [%]	Δ fuel consumption [g/kW h]	Δ fuel consumption [%]	The %NOx ratio with % fuel consumption difference of being benefited
							A. mineral Gp III base oil (constant)	Fade to fischer-tropsch gas oil from mineral gas oil	0.60	9	30.1	4.3	2.01
B. fischer-tropsch Gp III base oil (constant)	Fade to fischer-tropsch gas oil from mineral gas oil	0.53	11	27.0	3.9	2.86
							C. mineral gas oil (constant)	Fade to Fei-Tuo Gp III base oil from mineral Gp III base oil	0.26	5.2	7.73	1.1	4.66
D. fischer-tropsch gas oil (constant)	Fade to Fei-Tuo Gp III base oil from mineral Gp III base oil	0.19	4.3	4.70	0.7	6.14

Table 4 has illustrated two effects as can be seen: first effect is to represent in identical scope by the variation from mineral gas oil to Fisher-Tropsch derived gas oil on constant base oil lubricant; Second effect can be from finding out when constant gas oil exchanges lubricant compositions.Experiment A and B have illustrated that Fisher-Tropsch derived gas oil is to the beneficial effect of NOx discharging.

Experiment C has illustrated with the independent effect of independent change base oil or change fuel with D and has compared that the combination of fischer-tropsch gas oil and fischer-tropsch base oil has reduced oxynitride more.In addition, found when prolonging application during the time that use the combination of the present invention beneficial effect that discharging brings to NOx to maintain under the identical level, the discharging of mineral oil derived lubricant formulations then increases in time.

Claims (11)

1. be used for lubricant and the fuel composition bag of the combination of operating diesel machine, wherein said lubricant contains:

(i) paraffinic base oil, described paraffinic base oil is Fisher-Tropsch derived base oil and/or the poly-alpha olefins base oil of deriving, have greater than the paraffinicity of 80wt% paraffinic hydrocarbons with greater than the saturates content of 98wt%, with contain have n, the continuous series isoparaffin of n+1, n+2, n+3 and n+4 carbon atom and/or have n, n+2 and n+4 carbon atom and do not contain n+1 and the continuous series isoparaffin of n+3 carbon atom, wherein n is 15-40; Randomly

(ii) less than the other base oil of 20wt%, described other base oil is selected from mineral based paraffinic and naphthenic base oils and synthetic base oil; With

Wherein said fuel composition contains the Fisher-Tropsch derived paraffinic hydrocarbons gas oil component of 5-100wt%, and described Fisher-Tropsch derived paraffinic hydrocarbons gas oil component has greater than the paraffinicity of 80wt% paraffinic hydrocarbons with greater than the saturates content of 98wt%.

2. the lubricant of the combination of claim 1 and fuel composition bag, wherein said Fisher-Tropsch derived paraffinic hydrocarbons gas oil component comprise have n, the serial isoparaffin of n+1, n+2, n+3 and n+4 carbon atom and wherein n be 8-25.

3. lubricant and the fuel composition bag of claim 1 or 2 combination, the kinematic viscosity of wherein said paraffinic base oil under 100 ℃ is 3-25mm ²/ s.

4. lubricant and the fuel composition bag of claim 1 or 2 combination, the isoparaffin of wherein said fuel composition and the mass ratio of n-paraffin increase to that C18 increases and wherein said fuel composition contains less than the sulphur of 0.05%m/m with less than the aromatic hydrocarbons of 10wt% with the paraffinic hydrocarbons carbon number from C8 usually.

5. lubricant and the fuel composition bag of claim 1 or 2 combination, the alkyl branches number of each paraffin molecules of wherein said fuel composition is on average greater than 1.

6. lubricant and the fuel composition bag of claim 1 or 2 combination, wherein said fuel composition contains the isoparaffin of 50wt% at least.

7. lubricant and the fuel composition bag of claim 1 or 2 combination, the cetane value of wherein said fuel composition is at least 65.

8. engine configurations for generation of kinetic energy and heat energy, described engine configurations comprises: (a) contain the diesel engine of lubricant compositions, with fuel distribution and the stocking system that (b) links to each other with diesel engine, wherein said diesel lubrication agent contains:

(i) paraffinic base oil or oil base stock, described paraffinic base oil or oil base stock are Fisher-Tropsch derived base oil or oil base stock and/or poly-alpha olefins derive base oil or oil base stock, have greater than the paraffinicity of 80wt% paraffinic hydrocarbons with greater than the saturates content of 98wt%, with comprise have n, the serial isoparaffin of n+1, n+2, n+3 and n+4 carbon atom and/or have n, n+2 and n+4 carbon atom and do not contain n+1 and the serial isoparaffin of n+3 carbon atom, wherein n is 15-40 and randomly

The other base oil or the oil base stock that (ii) are less than 20wt%, described other base oil or oil base stock are selected from mineral based paraffinic and naphthenic base oils and synthetic base oil;

Wherein said paraffinic base oil or the oil base stock kinematic viscosity under 100 ℃ is 3-8mm ²/ s; With

Wherein said fuel distribution and stocking system contain the fuel composition of the Fisher-Tropsch derived paraffinic hydrocarbons gas oil component of 5-100wt%, and described Fisher-Tropsch derived paraffinic hydrocarbons gas oil component has greater than the paraffinicity of 80wt% paraffinic hydrocarbons with greater than the saturates content of 98wt%.

9. the carrier vehicle, water pump or the fixed generator that comprise the engine configurations of claim 8.

10. one kind is used for the method for generating electricity under the condition that reduces the nitrous oxides exhaust gas discharging, comprise the fuel composition operating diesel machine that uses the Fisher-Tropsch derived paraffinic hydrocarbons gas oil component contain 5-100wt%, described Fisher-Tropsch derived paraffinic hydrocarbons gas oil component has greater than the paraffinicity of 80wt% paraffinic hydrocarbons with greater than the saturates content of 98wt%; With make the lubricant compositions lubricating engine, wherein said lubricant compositions comprises:

(i) paraffinic base oil or oil base stock, described paraffinic base oil or oil base stock are Fisher-Tropsch derived base oil or oil base stock and/or poly-alpha olefins derive base oil or oil base stock, have greater than the paraffinicity of 80wt% paraffinic hydrocarbons with greater than the saturates content of 98wt%, with comprise have n, the serial isoparaffin of n+1, n+2, n+3 and n+4 carbon atom and/or have n, n+2 and n+4 carbon atom and do not contain n+1 and the serial isoparaffin of n+3 carbon atom, wherein n is 15-40; Randomly

The other base oil or the oil base stock that (ii) are less than 20wt%, described other base oil or oil base stock are selected from mineral based paraffinic and naphthenic base oils and synthetic base oil.

11. claim 1-7 each the lubricant of combination and the fuel composition bag for reducing the purposes of the oxynitride in the engine exhaust.

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