CN104371776A - Low-sulfur diesel with improved lubricity and method for increasing lubricity of low-sulfur diesel - Google Patents

Low-sulfur diesel with improved lubricity and method for increasing lubricity of low-sulfur diesel Download PDF

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CN104371776A
CN104371776A CN201310359210.5A CN201310359210A CN104371776A CN 104371776 A CN104371776 A CN 104371776A CN 201310359210 A CN201310359210 A CN 201310359210A CN 104371776 A CN104371776 A CN 104371776A
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amino
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oil
sulfur diesel
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CN104371776B (en
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蔺建民
黄燕民
李宝石
李航
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention provides a low-sulfur diesel with improved lubricity, which comprises low-sulfur diesel and a condensation reaction product of 10mg/kg-2000mg/kg amino polyprotic acid and amine. The method for improving the low-sulfur diesel is characterized in that the condensation reaction product of 10mg/kg-2000mg/kg amino polyprotic acid and amine is added in the low-sulfur diesel. The provided low-sulfur diesel has obvious improved lubricity, compared with amine which is directly used as a diesel oil anti-grinding agent and grease which is used as the diesel oil anti-grinding agent in prior art, the lubricity improvement effect of the diesel oil is obviously better.

Description

The method of the improved low-sulfur diesel-oil composition of a kind of oilness and raising Lubricity of Low-Sulfur Diesel Fuels
Technical field
The present invention relates to the method for the improved low-sulfur diesel-oil composition of a kind of oilness and raising Lubricity of Low-Sulfur Diesel Fuels.
Background technology
Along with countries in the world are to the pay attention to day by day of environmental issue, pollute to reduce diesel exhaust gas, producing high-quality clean diesel, having become the developing direction of modern petroleum refining industry.The features such as it is low that this diesel oil generally has sulphur content, low containing aromatic hydrocarbons, and cetane value is high, and cut is light.Research shows, sulphur is the most harmful element increasing CH, CO, particularly pellet (PM) in diesel engine emissions, so it is particularly important to improving topsoil to reduce sulphur content in diesel oil.The present U.S., Canadian diesel oil regulation all regulation derv fuel oil sulphur content is not more than 0.0015%, what European Countries was implemented at present meet, and derv fuel oil standard-required sulphur content that Europe V discharges is not more than 0.001%, require in the derv fuel oil standard that China implements at present that sulphur content is not more than 0.035%(state 3 emission request) and 0.005%(state 4 emission request will be not more than being transitioned into sulphur content in the recent period), such as Beijing, indivedual city implemented the derv fuel oil standard meeting state 4 emission request in 2008, and very soon implement state 5 emission request that sulphur content is not more than 0.001%.Harsher hydrogenation technique is generally have employed owing to producing this kind of diesel oil, polarity in diesel oil is all very low containing the content of oxygen, nitrogenous compound, the content of many rings, double ring arene is also less, thus the natural lubricity of diesel oil is reduced, having there are wearing and tearing as rotor pump (rotary pumps), proportioning pump (distributor pumps) in the oil injection pump causing some to rely on diesel oil itself to carry out lubricating, reduces their work-ing life.General high-frequency reciprocating experimental machine (HFRR) evaluates the average grinding defect diameter WS1.4 of diesel oil, if this value is more than 460 microns, thinks the poor lubricity of oil product.
In diesel oil, add additive can alleviate this problem.Cost is little, production is flexible, pollute the advantages such as few to use the method for additive to have, and is industrially paid attention to widely.
Diesel antiwear additive mostly is the derivative of fatty acid ester, acid amides or salt.EP773279 discloses and reacts the carboxylicesters prepared as diesel antiwear additive with dimeracid and hydramine.EP798364 discloses and reacts the salt or acid amides prepared as diesel antiwear additive with lipid acid and aliphatic amide.EP1209217 discloses C 6-C 50saturated fatty acid and dicarboxylic acid and short chain oils dissolubility is primary, secondary, the reaction product of tertiary amine is as diesel antiwear additive.WO9915607 discloses the reaction product of dimer (fatty acid) yl and epoxide as diesel antiwear additive.These technology are most with lipid acid or dimer fatty acid and hydramine, amine, epoxide reaction, and wherein some reaction raw materials cost is higher.CS275894, EP605857 disclose with natural fats and oils if rapeseed oil, sunflower oil, castor-oil plant wet goods are directly as diesel antiwear additive.Though these products have the advantages such as raw material is easy to get, price is more cheap, result of use is relatively poor.
Summary of the invention
The object of the invention is to based on prior art, provide a kind of oilness improved low-sulfur diesel-oil composition.
Low-sulfur diesel-oil composition provided by the invention contains the condensation reaction products of low-sulfur diesel-oil and amino polyprotonic acid and amine, and relative to 1kg low-sulfur diesel-oil, the content of the condensation reaction products of described amino polyprotonic acid and organic amine is 10mg-2000mg.
The present invention also provides a kind of method improving Lubricity of Low-Sulfur Diesel Fuels, be included in low-sulfur diesel-oil the condensation reaction products adding amino polyprotonic acid and amine, relative to 1kg low-sulfur diesel-oil, the add-on of the condensation reaction products of described amino polyprotonic acid and organic amine is 10mg-2000mg.
Low-sulfur diesel-oil composition provided by the invention due to containing the described condensation reaction products by amino polyprotonic acid and amine as diesel antiwear additive, therefore there is the oilness obviously improved compared with low-sulfur diesel-oil self, and use grease to compare as diesel antiwear additive with directly using amine as diesel antiwear additive and prior art, the improvement result of diesel fuel lubricity is also obviously better, therefore can more effectively prevent diesel motor from causing the wearing and tearing of pump because of the fuel of poor lubricity of burning.
Embodiment
Low-sulfur diesel-oil composition of the present invention contains the amino polyprotonic acid of low-sulfur diesel-oil and 10mg/kg-2000mg/kg and the condensation reaction products of amine.
In the present invention, the addition of the reaction product of amino polyprotonic acid and amine is the addition relative to 1 kilogram of low-sulfur diesel-oil.
Described " amino polyprotonic acid " refers to that, containing amino polycarboxylic acid in molecule, preferably amino number is 1-5, is more preferably 1-3.Described amino is all preferably that uncle is amino.The number of the hydroxy-acid group (-COOH) in described aminopolycarboxylic acid can be 2-6, is more preferably 2-5.Described hydroxy-acid group be more preferably in formyloxy, acetoxyl, propionyloxy and butyric acid base one or more, be particularly preferably acetoxyl and/or propionyloxy.The total number of carbon atoms of described amino polyprotonic acid is preferably 2-20, is more preferably 4-14.The specific examples of described aminopolycarboxylic acid includes but not limited to iminodiethanoic acid, complexon I, ethylenediamine tetraacetic acid (EDTA) (EDTA), ethylenediamine tetrapropionic acid(EDTP) (EDTP), 1,2-trimethylenedinitrilo-tertraacetic acid, 1,3-trimethylenedinitrilo-tertraacetic acid (PDTA), diethylene triamine pentacetic acid (DTPA) (DTPA), 1, one or more in 6-hexamethylene dinitrilo-tetraacetic acid, CDTA.
Described organic amine can be the various organic amines that can form amide structure with the carboxyl generation condensation reaction in amino polyprotonic acid, such as, can be have the structure shown in formula (1)
In formula (1), R 1and R 2be the group shown in H, formula (2), formula (3) or (4) independently, and R 1and R 2be asynchronously H.
In formula (2), x be 2 or 3, y be the integer of 0 to 5, R 3for C 1-C 30alkyl; Preferred y is the integer of 1 to 4, R 3for C 6-C 24alkyl.
In formula (3), x1 be 2 or 3, y1 be the integer of 0 to 5, R 4for C 1-C 30alkyl; Preferred y1 is the integer of 1 to 4, R 4for C 6-C 24alkyl.
In formula (4), y2 is the integer of 0 to 5, R 5for C 1-C 26alkyl.
For formula (2), preferably y is the integer of 1 to 3 further, R 3for C 8-C 22alkyl.This alkyl can be saturated alkyl, also can be the thiazolinyl with double bond or the aryl with phenyl ring.Alkyl can be straight chain normal chain alkyl, also can be the isomery alkyl with side chain, the example of this alkyl comprises n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base, n-docosane base; Isobutyl-, the tertiary butyl, isopentyl, neo-pentyl, isohexyl, different heptyl, iso-octyl (i.e. 2-ethylhexyl), different nonyl, isodecyl, Permethyl 99A. base, different tetradecyl, isocetyl, isooctadecane base and Isoeicosane base.The example of thiazolinyl comprises 9-octadecylene base.Example with the aryl of phenyl ring comprises phenmethyl (benzyl), styroyl and hydrocinnamyl.
When y equals 1, formula (2) is-CH 2cH 2nHR 3or-CH 2cH 2cH 2nHR 3, preferably-CH 2cH 2cH 2nHR 3group, R 3definition same as described above.The group of such as formula (2) can be,
-CH 2cH 2cH 2nHC 10h 21(3-(the positive last of the ten Heavenly stems is amino) propyl group),
-CH 2cH 2cH 2nHC 12h 25(3-(positive ten diamino) propyl group),
-CH 2cH 2cH 2nHC 14h 29(3-(positive ten tetraminos) propyl group),
-CH 2cH 2cH 2nHC 16h 33(3-(positive 16 is amino) propyl group),
-CH 2cH 2cH 2nHC 18h 37(3-(positive 18 amino) propyl group) and
-CH 2cH 2cH 2nHC 18h 35(3-(oil is amino) propyl group).
According to the present invention, for formula (3), preferred y1 is the integer of 1-5.The further preferably integer of x1 to be 2, y1 be 1-4, R 4with above-mentioned R 3definition identical.The group of such as formula (3) can be:
-CH 2CH 2NHCOC 11H 23，
-CH 2CH 2NHCOC 13H 27，
-CH 2CH 2NHCOC 15H 31，
-CH 2CH 2NHCOC 17H 35，
-CH 2CH 2NHCOC 17H 33，
-CH 2CH 2NHCH 2CH 2NHCOC 11H 23，
-CH 2CH 2NHCH 2CH 2NHCOC 13H 27，
-CH 2CH 2NHCH 2CH 2NHCOC 15H 31，
-CH 2CH 2NHCH 2CH 2NHCOC 17H 35，
-CH 2CH 2NHCH 2CH 2NHCOC 17H 33，
-CH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCOC 11H 23，
-CH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCOC 13H 27，
-CH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCOC 15H 31，
-CH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCOC 17H 35，
-CH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCOC 17H 33，
-CH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCOC 11H 23，
-CH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCOC 13H 27，
-CH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCOC 15H 31，
-CH 2cH 2nHCH 2cH 2nHCH 2cH 2nHCH 2cH 2nHCOC 17h 35with
-CH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCH 2CH 2NHCOC 17H 33。
According to composition provided by the invention, for formula (4), preferred y2 is the integer of 0-2.R 5with above-mentioned R 3definition identical.The group of such as formula (4) can be:
The preferred described organic amine of the present invention contains at least two NH groups or contains at least one NH and at least one C=C.Described NH group can be primary amino NH 2, also can be secondary amino group.Further preferably, described organic amine is NH 2(CH 2) mnHR ', NH 2r " and NH 2(CH 2) nnH 2in one or more and R " ' one or more in the acid amides that formed of COOH, wherein, m and n is 1-4 separately, is preferably 2 or 3; R ', R " and R " ' separately for carbon atom is the alkyl of 5-25, described alkyl preferably containing at least one C=C, is further preferably R ', R further " and R " ' be cocoyl or 9-octadecylene base separately.
The present invention particularly preferably described organic amine is N-cocoyl Edamine, N-cocoyl-1,3-trimethylene diamines, N-oil base Edamine, N-oil base-1,3-trimethylene diamines, 9-octadecenyl amine, coconut oil and diethylenetriamine in molar ratio 1:0.5-1 react the acid amides, coconut oil and the triethylene tetramine that are formed in molar ratio 1:0.3-1 react the acid amides, oleic acid and the diethylenetriamine that are formed in molar ratio 1:0.5-1 react the acid amides, oleic acid and the triethylene tetramine that are formed in molar ratio 1:0.3-1 react in the acid amides formed one or more.
The condensation reaction of amino polyprotonic acid and organic amine is generally 1:0.2-5 according to the number of carboxyl in amino polyprotonic acid and the mol ratio of organic amine, preferably 1:0.6-1.5.Temperature of reaction is generally 80-300 DEG C, preferred within 120-250 DEG C of scope further, preferably within 180-220 DEG C of scope.Reaction times is as the criterion to react fully, and can determine to react the degree of carrying out according to point water yield, the preferred reaction time is 5-30 hour.Reaction medium can be aromatic solvent as dimethylbenzene, ethylbenzene, aromatic diluent oil (boiling range is 159-185 DEG C), mineral oil (boiling point is more than 120 DEG C), naphthane, or their mixture.Solvent load is generally the 30-150 % by weight of reaction mass gross weight.Reaction also can without solvent.Available nitrogen protection in reaction system, or allow system carry out under reflux water-dividing condition.Reaction can without catalyzer, also can carry out under acidity or basic catalyst effect, an acidic catalyst is as sulfuric acid, phosphoric acid, tosic acid, acidic ion exchange resin, heteropolyacid, solid super-strong acid, acidic white earth, acidic molecular sieve etc., and basic catalyst is as NaOH, KOH, Ca (OH) 2, Mg (OH) 2, sodium methylate, potassium methylate, organic amine etc.Also can steam solvent at the end of reaction, then be deployed into heavy aromatic solvent the diluent use that solvent is 20-50 % by weight.In the present invention, the addition unification in compositions of additives and diesel oil is adjusted (i.e. not solvent-laden add-on) with dry dosage.
NH 2(CH 2) nnH 2with R " ' acid amides that formed of COOH can be obtained by various mode; such as can be commercially available; also can be obtained by condensation reaction according to existing method; the concrete operations of condensation reaction can with reference to the carrying out of above-mentioned amino polyprotonic acid and organic amine generation condensation reaction; can carry out with reference to known method, the present invention does not repeat them here yet.
According to use needs, low-sulfur diesel-oil composition provided by the invention can also contain other additive, as one or more in phenol type antioxidant, polymer amine type ashless dispersant, FLOW IMPROVERS, cetane number improver, metal passivator, static inhibitor, sanitas, rust-preventive agent, emulsion splitter etc.
Described polymer amine type ashless dispersant comprise in allyl butyrate imide and/or alkenyl succinic acid acid amides, mannich base type ashless dispersant, polyethers amine type ashless dispersant and polyolefine amine type ashless dispersant one or more.Described allyl butyrate imide and/or the polyolefin-based Succinic anhydried of base succinamide ashless dispersant such as number-average molecular weight at 500-3000 and/or the reaction product of succinic acid and amine, if domestic trade names are T151A(mono butonediimide), T151B(mono butonediimide), the two succimide of T152(), the two succimide of T154(), T155(poly succimide) and/or T161(poly succimide) etc.Import additive as OLOA-1200, LZ894, Infineum C9238,9237, Hitec644 etc.The polyolefin-based phenol of mannich base type ashless dispersant such as number-average molecular weight at 500-3000 and the condensation product of formaldehyde and amine; After described polyethers amine type ashless dispersant such as C8-C30 alkylphenol and oxyethane or propylene oxide adduction again with the product of amine condensation or C8-C30 alcohol and oxyethane or propylene oxide adduction after again with the product of amine condensation; Described polyolefine amine type ashless dispersant such as chlorinatedpolyolefins and amine react the polyolefin-based amine generated.
Described FLOW IMPROVERS is preferably containing polymkeric substance or the ethylene-vinyl acetate polymkeric substance of (methyl) acrylate.Cetane number improver can be nitric ether or superoxide, as isooctyl ester nitrate, ditertiary butyl peroxide etc.Specifically, metal passivator can be one or more in 124 Triazole and derivative, thiadiazoles and derivative thereof, oxine, hydrazides, beta-diketon, 'beta '-ketoester, Schiff's base (Schiff bases), organic polycarboxylic acid and derivative thereof.Because this solvability in biofuel of 124 Triazole is very unexcellent, therefore, in order to increase its solvability in biofuel, usually carry out modification to 124 Triazole, the method for modification mainly through introducing oil-soluble group as long chain hydrocarbon groups in 124 Triazole.Therefore, described 124 Triazole derivative can be the various derivatives that various solvability in biofuel is good compared with 124 Triazole itself.Concrete, one or more in the described 124 Triazole derivative product that can be the ammonium salt that formed of 124 Triazole and aliphatic amide and 124 Triazole, formaldehyde and aliphatic amide be obtained by mannich reaction.Concrete, metal passivator can be the ammonium salt that 124 Triazole and aliphatic amide are formed, the product that 124 Triazole, formaldehyde and aliphatic amide are obtained by mannich reaction, one or more in Schiff's base and organic polycarboxylic acid.Described ethylenediamine tetraacetic carboxylic acid can be ethylenediamine tetraacetic acid (EDTA) (EDTA), and described hydrazides can be N-salicylidene-N '-salicylyl hydrazine and/or N, N '-diacetyl adipyl two hydrazides.Described beta-diketon is as methyl ethyl diketone, and described 'beta '-ketoester is as etheric acid monooctyl ester.Described Schiff's base can be one or more in N, N '-two salicylidene-1，2-diaminoethane, N, N '-two salicylidene-1,2-propylene diamine, N, N '-two salicylidene-1,2-cyclohexanediamine, N, N '-two salicylidene-N '-methyl dipropylenetriamine.Described organic polycarboxylic acid and derivative thereof can be such as one or more in citric acid, tartrate, oxysuccinic acid, succsinic acid (succinic acid), toxilic acid, phytic acid etc. and derivative thereof.
In the present invention, described low-sulfur diesel-oil refers to that sulphur content is no more than the diesel oil of 350mg/kg preferably no more than 50mg/kg.Wherein sulphur content is recorded by ultraviolet fluorescent method (SH/T0689).Described low-sulfur diesel-oil generally can be obtained by the sulfur method such as hydrofining or hydrocracking.
The method of raising Lubricity of Low-Sulfur Diesel Fuels provided by the invention comprises, in low-sulfur diesel-oil, add the condensation reaction products of above-mentioned amino polyprotonic acid and amine, relative to 1kg low-sulfur diesel-oil, the add-on of the condensation reaction products of described amino polyprotonic acid and organic amine is 10mg-2000mg.
Under preferable case, relative to 1kg low-sulfur diesel-oil, the add-on of the condensation reaction products of described amino polyprotonic acid and organic amine is 20mg-1500mg, is more preferably 50mg-1000mg.The condensation reaction products of described amino polyprotonic acid and organic amine is described above, does not repeat them here.
The present invention is described further for the following examples.
Preparation example 1-5 is for illustration of the synthesis of the reaction product of amino polyprotonic acid and amine.
Preparation example 1
In three-necked bottle, add 116.2g N-cocoyl-1,3-trimethylene diamines and 35.0g ethylenediamine tetraacetic acid (EDTA) (EDTA), wherein the mol ratio of N-cocoyl-1,3-trimethylene diamines and ethylenediamine tetraacetic acid (EDTA) is 4:1, i.e. the mol ratio 1:1 of carboxyl in amine and amino polyprotonic acid.Heated and stirred to 190 DEG C, passes into nitrogen reaction 20h, and collects the water generated with collector, then cool to 120 DEG C, takes out 2h with a small amount of water generated except dereaction, collect watery thing 13.6g altogether, obtain reaction product 125.2g with vacuum pump pressure.
Preparation example 2
In three-necked bottle, add 129.8g N-oil base-1,3-trimethylene diamines and 38.2g complexon I (NTA), wherein the mol ratio of N-oil base-1,3-trimethylene diamines and complexon I is 2:1, i.e. carboxyl mol ratio 1:1.5 in amine and amino polyprotonic acid.Heated and stirred to 170 DEG C, passes into nitrogen reaction 18h, and collects the water generated with collector, then cool to 110 DEG C, takes out 2h with a small amount of water generated except dereaction, collect watery thing 6.6g altogether, obtain reaction product 149.4g with vacuum pump pressure.
Preparation example 3
In three-necked bottle, add 133.8g oleyl amine and 38.3g1,3-trimethylenedinitrilo-tertraacetic acid (PDTA), wherein the mol ratio of oleyl amine and 1,3-trimethylenedinitrilo-tertraacetic acid is 4:1, i.e. carboxyl mol ratio 1:1 in amine and amino polyprotonic acid.Heated and stirred to 200 DEG C, passes into nitrogen reaction 25h, and collects the water generated with collector, then cool to 120 DEG C, takes out 2h with a small amount of water generated except dereaction, collect watery thing 10.1g altogether, obtain reaction product 149.4g with vacuum pump pressure.
Preparation example 4
In three-necked bottle, add 186.2g oleic acid and triethylene tetramine reacts the acid amides and 35.0g ethylenediamine tetraacetic acid (EDTA) (EDTA) that are formed, wherein oleic acid and triethylene tetramine react the mol ratio of acid amides and the ethylenediamine tetraacetic acid (EDTA) formed is 3:1, i.e. the mol ratio 0.75:1 of carboxyl in organic amine and amino polyprotonic acid.Heated and stirred to 200 DEG C, passes into nitrogen reaction 20h, and collects the water generated with collector, then cool to 120 DEG C, takes out 2h with a small amount of water generated except dereaction, collect watery thing 12.8g altogether, obtain reaction product 162.2g with vacuum pump pressure.
Wherein, oleic acid and triethylene tetramine react the acid amides formed and prepare according to following step:
In a 500ml three-necked bottle, add 0.5mol oleic acid and 0.3mol triethylene tetramine heated and stirred to 130 DEG C, pass into nitrogen and blow water and react 5 hours.Product after dewatering, by infrared analysis product, finds the characteristic peak having amide group in reaction product.This reaction product directly reacts the acid amides that the formed condensation product for the preparation of amino polyprotonic acid of the present invention and organic amine as oleic acid and triethylene tetramine.
Preparation example 5
In three-necked bottle, add octadecylamine and 1,3-trimethylenedinitrilo-tertraacetic acid (PDTA), wherein the mol ratio of octadecylamine and 1,3-trimethylenedinitrilo-tertraacetic acid is 4:1, i.e. carboxyl mol ratio 1:1 in amine and amino polyprotonic acid.Heated and stirred to 200 DEG C, passes into nitrogen reaction 25h, and collects the water generated with collector, then cool to 120 DEG C, takes out 2h with a small amount of water generated except dereaction, obtain reaction product 150.1g with vacuum pump pressure.
Embodiment 1-12
Embodiment 1-12 is the result of use of additive in diesel oil that preparation example 1-5 obtains.
(diesel oil a) is evaluated with-10# mixed oil (diesel oil b), and its physicochemical property is in table 1 to select Sinopec Beijing Yanshan Mountain branch office 0# mixed oil.
The physicochemical property of table 1 diesel oil
Add HFRR method (ISO12156-1) the grinding defect diameter WS1.4 of diesel oil before and after agent in table 2, wherein less, the average oil film rate of formation of grinding defect diameter is larger, average friction coefficient is less, then the oilness of diesel oil is better.Most diesel oil standard such as European standard EN590-2009, Chinese derv fuel oil standard GB/T19147-2009, derv fuel oil Beijing provincial standard DB11/239-2007 is less than 460um(60 DEG C with grinding defect diameter (WS1.4) in the world at present) be the qualified foundation of diesel fuel lubricity.Valuator device is that the diesel fuel lubricity that PCS company of Britain produces evaluates instrument.
Comparative example 1-6
Using the application as diesel antiwear additive of reaction raw materials oleyl amine or rapeseed oil (according to CS275894, EP605857).
The condensation reaction products of the amino polyprotonic acid of table 2 and organic amine is to the improvement of diesel fuel lubricity
Can be found out by table 2, when condensation reaction products by amino polyprotonic acid and amine of the present invention uses as diesel antiwear additive, have the oilness improving low-sulfur diesel-oil and well improve effect, as a comparison, the improvement result of reaction raw materials amine to diesel fuel lubricity is poor; Grease is used as the effect of anti-wear agent also not as the present invention in prior art.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (16)

1. a low-sulfur diesel-oil composition, it is characterized in that, this low-sulfur diesel-oil composition contain low-sulfur diesel-oil and and the condensation reaction products of amino polyprotonic acid and organic amine, relative to 1kg low-sulfur diesel-oil, the content of the condensation reaction products of described amino polyprotonic acid and organic amine is 10mg-2000mg.
2. low-sulfur diesel-oil composition according to claim 1, wherein, relative to 1kg low-sulfur diesel-oil, the content of the condensation reaction products of described amino polyprotonic acid and organic amine is 100mg-500mg.
3. low-sulfur diesel-oil composition according to claim 1 and 2, wherein, number 1-5 amino in described amino polyprotonic acid, the number of hydroxy-acid group is 2-6, and described amino is tertiary amino; Described organic amine contains at least two NH groups or contains at least one NH and at least one C=C.
4. according to the low-sulfur diesel-oil composition in claim 1-3 described in any one, wherein, the total number of carbon atoms of described amino polyprotonic acid is 4-14, and hydroxy-acid group is one or more in formyloxy, acetoxyl, propionyloxy and butyric acid base, and described organic amine is NH 2(CH 2) mnHR ', NH 2r " and NH 2(CH 2) nnH 2in one or more and R " ' in the acid amides that formed of COOH one or more, wherein, m and n is 1-4, R separately ', R " and R " ' separately for carbon atom is the alkyl of 5-25.
5. the low-sulfur diesel-oil composition according to claim 3 or 4, wherein, number amino in described amino polyprotonic acid is 1-3, and the number of hydroxy-acid group is 2-5, hydroxy-acid group is acetoxyl and/or propionyloxy, R ', R " and R " ' be cocoyl or 9-octadecylene base separately.
6. low-sulfur diesel-oil composition according to claim 1, wherein, described amino polyprotonic acid is iminodiethanoic acid, complexon I, ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetrapropionic acid(EDTP), 1,2-trimethylenedinitrilo-tertraacetic acid, 1,3-trimethylenedinitrilo-tertraacetic acid, diethylene triamine pentacetic acid (DTPA), 1, one or more in 6-hexamethylene dinitrilo-tetraacetic acid, CDTA; Described organic amine is N-cocoyl Edamine, N-cocoyl-1,3-trimethylene diamines, N-oil base Edamine, N-oil base-1,3-trimethylene diamines, 9-octadecenyl amine, coconut oil and diethylenetriamine in molar ratio 1:0.5-1 react the acid amides, coconut oil and the triethylene tetramine that are formed in molar ratio 1:0.3-1 react the acid amides, oleic acid and the diethylenetriamine that are formed in molar ratio 1:0.5-1 react the acid amides, oleic acid and the triethylene tetramine that are formed in molar ratio 1:0.3-1 react in the acid amides formed one or more.
7. according to the low-sulfur diesel-oil composition in claim 3-6 described in any one, wherein, in the mol ratio of the described amino polyprotonic acid of the carboxyl in amino polyprotonic acid and organic amine for 1:0.6-1.5, the temperature of condensation reaction is 80-300 DEG C, and the time of condensation reaction is 5-30 hour.
8. low-sulfur diesel-oil composition according to claim 1, wherein, the sulphur content of described low-sulfur diesel-oil is lower than 350mg/kg.
9. one kind is improved the method for Lubricity of Low-Sulfur Diesel Fuels, the method is included in low-sulfur diesel-oil the condensation reaction products adding amino polyprotonic acid and amine, relative to 1kg low-sulfur diesel-oil, the add-on of the condensation reaction products of described amino polyprotonic acid and organic amine is 10mg-2000mg.
10. method according to claim 9, wherein, relative to 1kg low-sulfur diesel-oil, the addition of the condensation reaction products of described amino polyprotonic acid and organic amine is 100mg-500mg.
11. methods according to claim 9 or 10, wherein, number 1-5 amino in described amino polyprotonic acid, the number of hydroxy-acid group is 2-6, and described amino is tertiary amino; Described organic amine contains at least two NH groups or contains at least one NH and at least one C=C.
12. according to the method in claim 9-11 described in any one, and wherein, the total number of carbon atoms of described amino polyprotonic acid is 4-14, and hydroxy-acid group is one or more in formyloxy, acetoxyl, propionyloxy and butyric acid base, and described organic amine is NH 2(CH 2) mnHR ', NH 2r " and NH 2(CH 2) nnH 2in one or more and R " ' in the acid amides that formed of COOH one or more, wherein, m and n is 1-4, R separately ', R " and R " ' separately for carbon atom is the alkyl of 5-25.
13. methods according to claim 11 or 12, wherein, number amino in described amino polyprotonic acid is 1-3, and the number of hydroxy-acid group is 2-5, and hydroxy-acid group is acetoxyl and/or propionyloxy, R ', R " and R " ' be cocoyl or 9-octadecylene base separately.
14. methods according to claim 9, wherein, described amino polyprotonic acid is iminodiethanoic acid, complexon I, ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetrapropionic acid(EDTP), 1,2-trimethylenedinitrilo-tertraacetic acid, 1,3-trimethylenedinitrilo-tertraacetic acid, diethylene triamine pentacetic acid (DTPA), 1, one or more in 6-hexamethylene dinitrilo-tetraacetic acid, CDTA; Described organic amine is N-cocoyl Edamine, N-cocoyl-1,3-trimethylene diamines, N-oil base Edamine, N-oil base-1,3-trimethylene diamines, 9-octadecenyl amine, coconut oil and diethylenetriamine in molar ratio 1:0.5-1 react the acid amides, coconut oil and the triethylene tetramine that are formed in molar ratio 1:0.3-1 react the acid amides, oleic acid and the diethylenetriamine that are formed in molar ratio 1:0.5-1 react the acid amides, oleic acid and the triethylene tetramine that are formed in molar ratio 1:0.3-1 react in the acid amides formed one or more.
15. according to the method in claim 9-14 described in any one, wherein, in the mol ratio of the described amino polyprotonic acid of the carboxyl in amino polyprotonic acid and organic amine for 1:0.8-1.2, the temperature of condensation reaction is 80-300 DEG C, and the time of condensation reaction is 5-30 hour.
16. methods according to claim 9, wherein, the sulphur content of described low-sulfur diesel-oil is lower than 350mg/kg.
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