CN104334698A

CN104334698A - Bearing lubricants for pulverizing equipment

Info

Publication number: CN104334698A
Application number: CN201380029153.2A
Authority: CN
Inventors: E·S·阿库兹伟奇; J·N·芬奇; M·R·斯维克; F·M·库尼
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2012-04-04
Filing date: 2013-04-01
Publication date: 2015-02-04
Also published as: EP2834332A1; CA2869329A1; WO2013151911A1; JP2015512468A; AU2013243735A1; KR20140143823A; AU2013243735B2; US20150094243A1

Abstract

The invention relates to a method of lubricating the bearings of solid fuel pulverizers, for example, coal pulverizers. The method involves supplying to the bearings a lubricating composition designed to have superior performance compared to conventional coal pulverizer bearing lubricants. The invention also provides a bearing lubricant for a coal pulverizer as well as its use in coal pulverizing equipment to improve the service life and/or durability of bearings in coal pulverizing equipment. The invention also provides an additive composition for use in a bearing lubricant for a coal pulverizer, as well as the use of the additive composition to improve the service life and/or performance of the bearing lubricant.

Description

For the bearing lubricant of disintegrating apparatus

Invention field

The present invention relates to the method for lubricating solid fuel pulverizer as the bearing of coal pulverizer.The method relates to feed lubricating composition in bearing, and described lubricating composition is designed to have the excellent in performance compared with machine bearing lubricant broken with conventional pulverized-coal.The present invention is also provided for the bearing lubricant of coal pulverizer and it improves the work-ing life of the bearing in coal disintegrating apparatus and/or the purposes of weather resistance in coal disintegrating apparatus.The present invention is also provided for the compositions of additives in coal pulverizer bearing lubricant, and this compositions of additives improves the work-ing life of bearing lubricant and/or the purposes of performance.

background of invention

Know pulverizer for reducing solid-fuelled granularity to allow that solid fuel burns in stove.Pulverizer uses some combinations impacted, rub and crush to make solid fuel be down to specified particle size.A few class pulverizer can be used for the granularity being suitable for as coal dust is broken into by solid fuel burning in stove.These can comprise tube mill (ball-tube mill), impact mill, masher, ball race mill machine (ball race mill) and ring roll mill or ball mill.But, the most normally use the ball mill with combined and staged equipment to pulverize solid fuel to allow transport, the drying of the pulverized fuel carried secretly in the air stream and directly to burn.Still need mill load and the roller life-span of the bearing improving these pulverizers.

Except the mill load improved, another factor of the roller life-span deterioration of bearing is comprised flow into and the solid fuel dust polluting bearing and lubricant as coal dust.Usually, pulverizer has the interface be exposed under atmospheric condition between rotating component and stationary shaft, and the differential pressure on assembly allows that coal dust such as flows in the assembly holding bearing.The entering of coal on this interface, it allows that axle extends through and rotates relative to Journal housing, pollution lubricating agent and shaft bearing, therefore makes the roller life-span deterioration of shaft bearing.

Some routes relate to design to reduce the complicated machinery sealing of dust inlet and expensive new installation.But, these solutions for the existing installation used without conduct.

Therefore, still need the method in the bearing roller life-span of improving in these pulverizers and lubricant and additive-package, it promotes the mill load of raising and prevents the infringement from bearing pollution, therefore allows and more effectively uses existing installation and do not need expensive repacking and improvement.

summary of the invention

The invention provides the method for the bearing of lubricating solid fuel pulverizer.The method relates to the lubricating composition feeding in bearing and design the excellent in performance had compared with conventional solid fuel pulverizer bearing lubricant.The design of this lubricating composition has the dust loading capacity of improvement, in other words, design this lubricant with severe condition seen in pulverizer, comprise and to perform better than traditional lubrication agent under the condition relating to a large amount of environment dust entered in lubricant and/or to continue more of a specified duration.The present invention also provides pulverizer bearing lubricant and in disintegrating apparatus, improves the work-ing life of the bearing in disintegrating apparatus and/or the purposes of weather resistance.The present invention is also provided for the compositions of additives in pulverizer bearing lubricant, and compositions of additives improves the work-ing life of bearing lubricant and/or the purposes of performance.In some embodiments, solid fuel pulverizer described herein is coal pulverizer.

Lubricating composition of the present invention comprises: (a) has the oil of lubricant viscosity, b () P contained compound and (c) nitrogenous dispersion agent, wherein P contained compound and nitrogenous dispersion agent one work the better performance of allowing in pulverizer bearing lubricant.In some embodiments, composition comprises (d) sulfocompound further.

In some embodiments, the present invention relates to mineral base oil lubricant.In other embodiments, the present invention relates to synthesis base oil lubricant.

The invention provides various P contained compound, comprise alkyl phosphite, phosphoric acid ester, the amine salt of phosphoric acid ester or its some combinations.In some embodiments, P contained compound comprises alkyl phosphite.

The invention provides various nitrogenous dispersion agent, comprise polyetheramine, boration succinimide dispersants, non-boration succinimide dispersants, comprise the Mannich dispersant of reaction product of (i), (ii) and (iii): (i) dialkylamine, (ii) aldehyde, (iii) alkyl fortified phenol, and any combination of various nitrogenous dispersion agent.In some embodiments, nitrogenous dispersion agent comprises non-boration succinimide dispersants.The present invention further provides the lubricant containing alkyl phosphite and non-boration succinimide dispersants.

In in these embodiments any one, P contained compound can based on being present in lubricant compositions without oil with 0.25 or 0.5 to 2.0 or 1.0 % by weight, and nitrogenous dispersion agent is present in lubricant compositions with 0.1 or 0.5 to 2.0 or 1.0 % by weight, describedly also to can be described as based on active substance in this article based on without oil.

detailed Description Of The Invention

Set forth below by indefiniteness and describe each characteristic sum embodiment of the present invention.

pulverizer and lubricating method

Be applicable to pulverizer of the present invention unduly limited.Pulverizer can be described as the device that can be used for affecting ground material usually.More specifically, the example of the various kinds of equipment of the grinding for carrying out many different kinds materials is had in prior art.On this point, in many cases, the distinguished difference that there is textural property between each pulverizer can be found.The existence of this kind of difference major part can apply relevant various functional requirements owing to each use with crusher design again.Such as, be ready to use in the pulverizer of the particular type of embody rule in selection, one of principal element of consideration is the character of the material treating to grind in a device.Coal is this material a kind of, wherein needs its grinding to be applicable in some application to make it.In addition, the power generation system of combustion of fossil fuel represents this application a kind of, wherein wants to use coal as fuel source, and wherein exists coal grinding, namely pulverize to make it be applicable to this object, namely for the requirement in coal combustion power generation system.Therefore, in some embodiments, be coal pulverizer for pulverizer of the present invention.

In some embodiments, pulverizer of the present invention can comprise the material feeder for being fed by solid fuel in pulverizer, for the equipment that solid fuel is pulverized, for the distribution system of dispense solid fuel after its pulverizing, the stove burnt treated wherein by solid fuel, and controls for the necessity of the proper operation carrying out the power generation system of ringing solid fuel ignition.Herein particularly importantly for by equipment as broken in coal dust for solid fuel.

In some embodiments, pulverizer of the present invention is ball mill.Ball mill can be made up of such as lower component substantially: install grinding stage with the main part rotated, with grinding stage acting in conjunction to carry out multiple mixing rolls of the solid-fuelled grinding be placed in therebetween, for solid fuel to be comminuted being fed the solid fuel feeding mechanism of ball grinder interior, with for air required between the latter's working life being fed the air supply device of ball grinder interior.According to the operator scheme of this ball mill, enter solid fuel in ball mill and pulverize by the acting in conjunction of mixing roll and grinding stage.After pulverizing, solid fuel particle is outwards thrown by centrifugal force, thus particle is fed in the airflow entered in ball mill.The airflow comprising now efflorescence solid fuel particle flows through zigzag path, and described zigzag path is positioned partially in ball mill partially by the inflector assembly of suitable load and sets up.When airflow and solid fuel particle are along above-mentioned zigzag path flowing, the zig zag be included in wherein carries out being separated of thick solid fuel particle and airflow.Then these thick solid fuel particles suitably return grinding stage to pulverize further, and thin solid fuel particle is carried through ball mill in the air stream simultaneously, and together with air from wherein leaving.Each ball mill also has the bearing relevant with mixing roll and grinding stage and/or their mounting block (mount) usually, such as head bearing and lower bearing.

Each pulverizer also has oiling system usually to be fed by lubricant in its bearing, comprises head bearing and the lower bearing of described ball mill, and findable all various bearings in on-the-spot all kinds of pulverizer used.

The invention provides the lubricant compositions of the bearing for solid fuel pulverizer, the method for lubricating the bearing of coal pulverizer by feeding described lubricant compositions in described bearing is also provided.Be described in hereinafter for the lubricant compositions in the present invention.

In some embodiments, the inventive method relates in described lubricant compositions infeed coal pulverizer.In some embodiments, the inventive method relates in described lubricant compositions infeed ball milling formula pulverizer.In some embodiments, the inventive method relates in described lubricant compositions infeed ball milling formula coal pulverizer.In some embodiments, the inventive method relates in the head bearing of described lubricant compositions infeed pulverizer.In some embodiments, the inventive method relates in the lower bearing of described lubricant compositions infeed pulverizer.In some embodiments, the inventive method relates to the head bearing and the lower bearing that described lubricant compositions are fed pulverizer, or in all bearings even in pulverizer.

lubricant compositions

The present invention includes the bearing lubrication composition be made up of following component: (a) has the oil of lubricant viscosity, b () P contained compound and (c) nitrogenous dispersion agent, wherein P contained compound and nitrogenous dispersion agent one work to allow good performance in pulverizer bearing lubricant.The present invention is also provided for the compositions of additives in pulverizer bearing lubricant, described compositions of additives is made up of following component: the thinner that (a) is optional, it can for having oil or the solvent of lubricant viscosity, (b) P contained compound, (c) nitrogenous dispersion agent, wherein P contained compound and nitrogenous dispersion agent one work to allow good performance in pulverizer bearing lubricant.In some embodiments, composition comprises (d) sulfocompound further.

In some embodiments, lubricant compositions comprises and (means not comprise thinning oil or solvent based on active substance, but think that component is based on pure) be 0.01-5.0, or 0.25-5.0, or 0.5-5.0, or 0.5-4.0,0.75-3.0,0.9-2.0, or 1-2, or even 1 or 2 % by weight P contained compound.In some embodiments, lubricant compositions comprises to be enough to be supplied to total lubricant compositions 0.01-5.0, or 0.025-0.5 or 0.025-0.25, or the P contained compound of the amount of 0.05-0.1 % by weight phosphorus.

In some embodiments, it is 0.01 or 0.1 or 0.25 to 10 or 5 or 4 that lubricant compositions comprises based on active substance, or 0.01 or 0.1 or 0.25-5, or 0.1-1.0, or 0.4 to 2.0 or 2.5, or the nitrogenous dispersion agent of 0.5-2.0 % by weight.

In some embodiments, P contained compound and nitrogenous dispersion agent are with 1:10-10:1, or 1:4-4:1, or 1:2-4:1, or 1:1-3:1, or the ratio of even about 2:1 is present in lubricant compositions, wherein than for thinking weight ratio based on non-activity material.In some embodiments, P contained compound and nitrogenous dispersion agent with 0.5:1-4:1, or and/or ratio to about 0.5:1,1:1,1.2:1,2:1 or 4:1 be present in lubricant compositions, wherein than for thinking based on the weight ratio without oil.

there is the oil of lubricant viscosity

A kind of component of the present composition is the oil with lubricant viscosity, and it for lubricant compositions, with primary amount, or for enriched material and/or compositions of additives, can exist with concentrate forming amount.

Suitable oil comprises natural and ucon oil and composition thereof.Preparing in lubricant completely, the oil with lubricant viscosity exists with primary amount (being namely greater than the amount of 50 % by weight) usually.Usually, have the 75-95 % by weight of oil with total composition of lubricant viscosity, the amount being usually greater than 80 % by weight exists.Base oil component forms 100 weight parts (pbw) of total composition usually, and wherein the pbw scope of other component is to consider that this 100pbw base oil provides.In other embodiments, provide the pbw scope of various component (comprising base oil) to make the pbw summation of all components be 100, therefore pbw value equals % by weight value.Can obtain with any one method about the pbw scope that hereinafter described various component provides, but, in most embodiment, should be read them to equal % by weight value.

The oil with lubricant viscosity can comprise natural and synthetic oil, derived from hydrocracking, hydrogenation and hydrorefined oil, and non-refining, refining and refining oil or its mixture.Non-refining oil is those that directly obtained by natural or synthesis source, and it is usually without (or through seldom) purification processes further.Refining oil is similar to non-refining oil, unlike they being processed to improve one or more performances further in one or more purification step.Purification techniques is as known in the art, and comprises solvent extraction, second distillation, acid or alkali extraction, filtration, diafiltration etc.Refining oil is also referred to as regeneration or reprocessed oils again, obtained, and the technology usually by being intended to remove useless additive and oil decomposition product is processed in addition by those the method be similar to for obtaining refining oil.

Natural oil as the oil with lubricant viscosity comprises animal oil, vegetables oil (such as Viscotrol C, lard), mineral lubricating oils is as the solvent treatment of liquid petroleum and paraffinic hydrocarbons, naphthenic hydrocarbon and combination chain alkane naphthenic type or acid treatment mineral lubricating oils, with the oil derived from coal or shale, or its mixture.

The synthetic oil with lubricant viscosity comprises hydrocarbon ils as polymerization and copolyolefine (such as polybutene, polypropylene, propylene isobutylene copolymers); Poly-(1-hexene), poly-(1-octene), poly-(1-decene) and composition thereof; Alkylbenzene (such as dodecylbenzene, Tetradecylbenzene, dinonyl benzene, two-(2-ethylhexyl) benzene); Polyphenyl (such as biphenyl, terphenyl, alkylated polyphenyls); Alkylated dipheny ethers and alkylated diphenyl sulfides and derivative, analogue and homologue, or its mixture.In some embodiments, for the oil with lubricant viscosity in the present invention for comprising the synthetic oil of polymerization polyisobutene, in some embodiments, for the oil with lubricant viscosity in the present invention for comprising the synthetic oil of polymerization polyisobutene and polyalphaolefin.

The another kind of synthetic oil with lubricant viscosity comprises the polyol ester, dicarboxylic ester, the liquid ester (such as the diethyl ester of Tritolyl Phosphate, tricresyl phosphate octyl group ester and decylphosphonic acid) of phosphoric acid or the polytetrahydrofuran that are different from alkyl end-blocking polyoxyalkylene polyol as disclosed herein.The conventional oil of synthesis with lubricant viscosity also comprises those that prepared by fischer-tropsch reaction, can be hydroisomerization Fischer-Tropsch hydrocarbon or wax usually.In one embodiment, the oil with lubricant viscosity by Fischer-Tropsch gas to the preparation of liquid synthesis program and other gas to liquid oil.

The oil with lubricant viscosity can define further as described in American Petroleum Institute (API) Base Oil Interchangeability Guidelines.Five groups of base oils are as follows: group I (sulphur content >0.03 % by weight, and/or <90 % by weight saturates, viscosity index 80-120); Group II (sulphur content≤0.03 % by weight, and >=90 % by weight saturatess, viscosity index 80-120); Group III (sulphur content≤0.03 % by weight, and >=90 % by weight saturatess, viscosity index >=120); Group IV (all polyalphaolefins, or PAO is as PAO-2, PAO-4, PAO-5, PAO-6, PAO-7 or PAO-8); With group V.The oil with lubricant viscosity comprises API group I, group II, group III, group IV, group V oil or its mixture.In one embodiment, the oil with lubricant viscosity is API group I, group II, group III, group IV oil or its mixture.As selection, the oil with lubricant viscosity is generally API group II, group III or organizes IV oil or its mixture.

In some embodiments, lubricating oil component of the present invention comprises group II or organizes III base oil or its combination.These are classification that API (American Petroleum Institute) establishes.Group III oil comprises <0.03% sulphur and >90% saturates and has the viscosity index of >120.Group II oil has the viscosity index of 80-120 and comprises <0.03% sulphur and >90% saturates.Oil also can derived from the hydroisomerization of wax as slack wax or Fischer Tropsch waxes.This kind of " gas is to liquid " oil classifies as group III usually.

The present composition can comprise the group I base oil of a tittle and even organize IV and group V base oil.Polyalphaolefin classifies as group IV.Group V comprises " other base oils all ".But in some embodiments, lubricating oil component of the present invention comprises no more than 20,10,5 or even 1 % by weight group of I base oil.These limit are also applicable to group IV or group V base oil.In other embodiments, lubricating oil in the present composition is present in at least 60,70,80,90 or even 95 % by weight groups of II and/or group III base oil.In some embodiments, the lubricating oil be present in the present composition is substantially only group II and/or group III base oil, wherein can there is the base oil of other type a small amount of, but not be the performance of remarkably influenced total composition or the amount of behavior.

In some embodiments, the present composition comprises group I and/or the group II base oil of a tittle.In other embodiments, the present composition is that the oil wherein with lubricant viscosity mainly organizes I and/or group II base oil, or is group I and/or group II base oil even substantially, or is even only the lubricating composition of group I and/or group II base oil.

The oil described in various with lubricant viscosity can be used alone or in combination.There is the oil of lubricant viscosity with about 70 % by weight to about 99 % by weight of lubricant, in another embodiment, about 75 % by weight to about 98 % by weight, in another embodiment, about 88 % by weight to about 97 % by weight use.

p contained compound

P contained compound is comprised for the composition in the present invention.

In some embodiments, P contained compound is phosphite.Suitable phosphite comprises and has at least one and have 4 or more, or 8 or more, or those of the alkyl of 12 an or more carbon atom.Carbonatoms object typical range on alkyl comprises 8-30, or 10-24, or 12-22, or 14-20, or 16-18.Phosphite can be that single alkyl replaces phosphite, dialkyl replaces phosphite or trialkyl replaces phosphite.

In one embodiment, phosphite is not sulfur-bearing, and namely phosphite is not thiophosphorous acid salt.

There is at least one phosphite with the alkyl of 4 or more carbon atoms can be expressed from the next:

Or

Wherein R ³, R ⁴and R ⁵in at least one can for comprising the alkyl of at least 4 carbon atoms, and other can be hydrogen or alkyl.In one embodiment, R ³, R ⁴and R ⁵be alkyl.Alkyl can be alkyl, cycloalkyl, aryl, acyclic group or its mixture.There are all three radicals R ³, R ⁴and R ⁵formula in, compound can be trialkyl replace phosphite, i.e. R ³, R ⁴and R ⁵it is all alkyl.

Alkyl can be linear or branching, is generally linear, and is saturated or undersaturated, usually saturated.About R ³, R ⁴and R ⁵the example of alkyl comprise octyl group, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, vaccenic acid base, nonadecyl, eicosyl or its mixture.

In some embodiments, P contained compound is the amine salt (amine salt of the hydrocarbon ester of phosphoric acid) of phosphoric acid hydrocarbon ester.The amine salt of phosphoric acid hydrocarbon ester can derived from the amine salt of phosphoric acid ester.The amine salt of phosphoric acid hydrocarbon ester can be expressed from the next:

Wherein: R ³and R ⁴can be hydrogen or usually comprise 4-40 independently, or 6-30, or 6-18, or the hydrocarbon of 8-18 carbon atom, condition is at least one is hydrocarbyl group; And R ⁵, R ⁶, R ⁷and R ⁸can be hydrogen or alkyl independently, condition is at least one be alkyl.R ³and/or R ⁴alkyl can be linear, branching or ring-type.

About R ³and/or R ⁴the example of alkyl comprise straight chain or branched-alkyl, comprise methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.Other example comprises 2-ethylhexyl, 4-methyl-2-amyl group and sec.-propyl.

About R ³and/or R ⁴the example of cyclic hydrocarbon group comprise cyclopentyl, cyclohexyl, suberyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl, diethyl cyclohexyl, methylcycloheptyl, dimethyl-cyclopentyl, methylethyl suberyl and diethyl suberyl.

In one embodiment, phosphoric acid salt can be the amine salt of the mixture of monoalkyl and dialkyl phosphate.Monoalkyl and dialkyl group can be linear or branching.

The amine salt of phosphoric acid hydrocarbon ester can derived from amine, such as primary amine, secondary amine, tertiary amine or its mixture.Amine can be aliphatic or ring-type, aromatics or non-aromatic, normally aliphatic.In one embodiment, amine comprises aliphatic amine, such as tertiary aliphatic primary amine.

The example of appropriate primary comprises ethamine, propylamine, butylamine, 2 ethyl hexylamine, two (2-ethylhexyl) amine, octylame and amino dodecane, and aliphatic amide is as n-octyl amine, n-Decylamine, n-dodecylamine, positive tetradecy lamine, hexadecylamine, octadecyl amine and oleyl amine.Other useful aliphatic amide comprises commercially available aliphatic amide, such as amine (can by Akzo Chemicals, Chicago, the product that Illinois obtains), such as Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein letter names relate to fat group, such as cocoyl, oil base, tallow base or stearyl.

The example of suitable secondary amine comprise dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, two heptyl amices, methyl ethyl-amine, ethyl butyl amine, N-methyl isophthalic acid-amino-cyclohexanecarboxylic, 2C and ethyl amylamine.Secondary amine can be cyclammonium, such as piperidines, piperazine and morpholine.

The example of tertiary amine comprise three-n-Butyl Amine 99, three-n-octyl amine, three-decyl amine, three-lauryl amine, three-cetylamine and dimethyloleylamine ( dMOD).

In one embodiment, amine is the form of mixture.The example of suitable amine mixt comprises the primary t-alkyl-amine that (i) has 11-14 carbon atom, and (ii) has the primary t-alkyl-amine of 14-18 carbon atom, or (iii) has the primary t-alkyl-amine of 18-22 carbon atom.Other example of primary t-alkyl-amine comprises TERTIARY BUTYL AMINE, tertiary hexylamine, tert-Octylamine (such as 1,1-dimethylhexylamine), tertiary decyl amine (such as 1,1-dimethyl octylame), tertiary amino dodecane, tertiary tetradecy lamine, tertiary cetylamine, tertiary stearylamine, uncle two tetradecy lamine and uncle two stearylamine.

In one embodiment, useful amine mixt be " 81R " or " jMT ". 81R and jMT (the two is produced by Rohm & Haas and sells) is respectively C ₁₁-C ₁₄primary t-alkyl-amine and C ₁₈-C ₂₂the mixture of primary t-alkyl-amine.

The amine salt of phosphoric acid hydrocarbon ester can as United States Patent (USP) 6, and 468, prepare described in 946.10th hurdle 15-63 line description forms phosphoric acid ester by phosphorus compound reaction, reacts thereafter the amine salt to form phosphoric acid hydrocarbon ester with amine.10th hurdle the 64th walks between the 12nd hurdle the 23rd line description Vanadium Pentoxide in FLAKES and alcohol (having 4-13 carbon atom) and reacts, (usual with amine thereafter 81-R) reaction forms the preparation embodiment of the amine salt of phosphoric acid hydrocarbon ester.

Suitable P contained compound also comprises the alkyl amine salt of dialkyl dithiophosphoric acid.The example of the alkyl amine salt of dialkyl dithiophosphoric acid is expressed from the next:

Wherein R ²⁶and R ²⁷be branching or linear alkyl independently.R ²⁶and R ²⁷comprise about 3 to about 30, preferably about 4 to about 25, more preferably from about 5 to about 20, most preferably from about 6 to about 19 carbon atoms.R ²³, R ²⁴and R ²⁵as mentioned above.

In some embodiments, the alkyl amine salt of dialkyl dithiophosphoric acid includes but not limited to the reaction product of diheptyl or dioctyl or dinonyl phosphorodithioic acid and quadrol, morpholine or Primene 81R or its mixture.

P contained compound can with the 0.01-5 % by weight of described composition, or 0.1-3 % by weight, or 0.2-1.5 % by weight, or 0.25-1 % by weight, or 0.5-1 % by weight exists.

nitrogenous dispersion agent

Comprise nitrogenous dispersion agent for the composition in the present invention, it is in some embodiments for alkyl replaces nitrogenous additive.Replace nitrogenous additive for the suitable alkyl in the present invention and comprise the additive being sometimes referred to as ashless dispersant.(although in for fuel applications time, these additives are commonly referred to fuel detergent) that dispersion agent is normally known in lubricant and fuel area.Suitable material mainly comprises and is called ashless dispersant and polymeric dispersant.Ashless dispersant appellation like this is because they do not comprise metal when providing, and does not therefore contribute vitriol ash when adding in lubricant.But certainly, when they being added in the lubricant comprising containing metal species, they may certain and environment metal interaction.The feature of ashless dispersant is connected to the polar group on higher molecular weight hydrocarbon chain.The example of this kind of material comprises succinimide dispersants, Mannich dispersant and berated derivatives thereof.

Be sometimes referred to as the reaction product that the Mannich dispersant of Mannich base dispersants or Mannich purification agent are alkyl fortified phenol, aldehyde and amine or ammonia.The hydrocarbyl substituent of alkyl fortified phenol can have 10-400,30-180,10 or 40 to 110 carbon atoms.This hydrocarbyl substituent can such as, derived from alkene or polyolefine, 1-decene, and it is commercially available.

The polyolefine that can form hydrocarbyl substituent can such as make polymerizing olefin monomers by the polymerization process known and prepare, and is also commercially available.Olefinic monomer comprises monoolefine, comprises the monoolefine with 2-10 carbon atom, such as ethene, propylene, 1-butylene, iso-butylene and 1-decene.The C4 refinery stream of monoolefine source for having 35-75 % by weight butene content and 30-60 % by weight iso-butylene content be particularly useful.Useful olefinic monomer also comprises diolefine, such as isoprene and 1,3-butadiene.Olefinic monomer also can comprise two or more monoolefines, two or more diolefine, or the mixture of one or more monoolefines and one or more diolefine.It is 140-5000, in another case 400-2500 that useful polyolefine comprises number-average molecular weight, in another case the polyisobutene of 140 or 500 to 1500.Polyisobutene can have 5-69%, in a second situation 50-69%, in the third case the vinylidene double bond of 50-95%.Polyolefine can be the homopolymer prepared by single olefinic monomer or the multipolymer prepared by the mixture of two or more olefinic monomers.What also can be used as hydrocarbyl substituent source has two or more homopolymer, two or more multipolymers, or the mixture of one or more homopolymer and one or more multipolymers.The aforementioned description of suitable alkyl or polyolefine group is also applicable to the hydrocarbyl substituent of the succinimide dispersants hereafter described in detail.

The above-mentioned alkene of phenol or polyolefine are prepared as polyisobutene or polypropylene alkylation by using the alkylation known by the alkyl fortified phenol for the preparation of Mannich dispersant.

Aldehyde for the formation of Mannich dispersant can have 1-10 carbon atom, and is generally formaldehyde or its reactive equivalent as formalin or paraformaldehyde.

Amine for the formation of Mannich dispersant can be monoamine or polyamines, comprises hereafter about those materials that succinimide dispersants describes, comprises the alkanolamine with one or more hydroxyl.Useful amine comprises thanomin, diethanolamine, methylamine, dimethylamine, quadrol, dimethylamino propylamine, diethylenetriamine and 2-(2-aminoethylamino) ethanol.Mannich dispersant can as U.S. Patent No. 5, and 697, prepare by making alkyl fortified phenol, aldehyde and amine react described in 988.In one embodiment, Mannich reaction products is prepared by derived from the alkylphenol of polyisobutene, formaldehyde and amine, and described amine is uncle's monoamine, secondary monoamine or Alkylenediamine, particularly quadrol or dimethylamine.In one embodiment, alkylphenol can such as be greater than 50 by having, be greater than 70 or be greater than 75% terminal vinylidene high vinylidene polyisobutylenes (i.e. the polyisobutene molecule with vinylidene terminal group of this percentage composition) preparation.The aforementioned description of amine is also suitable for hereinafter described for the preparation of the description of the amine of succinimide dispersants.

In one embodiment, Mannich dispersant comprises the reactive equivalent of alkyl fortified phenol, formaldehyde or formaldehyde and the reaction product of uncle or secondary amine.In one embodiment, Mannich dispersant comprises the reactive equivalent of polyisobutene fortified phenol, formaldehyde or formaldehyde and the reaction product of dimethylamine.

As used herein, term " hydrocarbyl substituent " or " alkyl " use with its conventional meaning well known to those skilled in the art.Specifically, it refers to have the carbon atom that is connected directly between on molecule rest part and mainly has the group of hydrocarbon character.The example of alkyl comprises: hydrocarbon substituent, comprises aliphatic series, alicyclic and aromatic substituent; The hydrocarbon substituent replaced, namely contains the substituting group of the non-hydrocarbon not changing substituent main hydrocarbon character in the context of the present invention; With assorted substituting group, namely there is main hydrocarbon character similarly, but containing the substituting group being different from carbon in ring or chain.The more specific definition of term " hydrocarbyl substituent " or " alkyl " finds in [0137]-[0141] section of disclosed application US 2010/0197536.

It is succinimide dispersants that another suitable alkyl replaces nitrogenous additive, and also can be described as succinimide fuel detergent.In one embodiment, succinimide dispersants be Hydrocarbyl-substituted succinic acid anhydrides or its reactive equivalent (such as acid anhydride, ester or acyl halide) with amine as the condensation product of polyethylene polyamine.Succinimide dispersants usually can be considered and comprises number of chemical structure, generally includes:

Wherein R ¹be alkyl independently of one another, be generally the molecular weight (M based on polyisobutene precursor with 500-5000 _n) polyisobutylene group, and R ²for alkylidene group, be generally ethylidene (C ₂h ₄).This quasi-molecule is usually derived from the reaction of alkenyl acylating agent and polyamines, and except the simple imide structure shown in above, the multiple key between two structure divisions is possible, comprises multiple acid amides and quaternary ammonium salt.In above structure, amine moiety is shown as alkylene polyamine, but also can use other aliphatic series and aromatics list-and polyamines, comprise above and hereinafter described those.In addition, R ¹the multiple key pattern of group on imide structure is possible, comprises various ring key.The carbonyl of acylating agent can be 1:0.5-1:3, in other cases 1:1-1:2.75 or 1:1.5-1:2.5 with the ratio of the nitrogen-atoms of amine.Succinimide dispersants is more completely described in United States Patent (USP) 4,234,435 and 3,172,892 and EP 0355895 in.

Succinimide dispersants also can be described as to be prepared by Hydrocarbyl-substituted succinic acid acylating agent, and it is again by so-called " chlorine " route or by so-called " heat " or the preparation of " direct alkylation " route.These routes are described in detail in open application US 2005-0202981, in 0014-0017 section.Direct alkylation or low chlorine route are also described in United States Patent (USP) 6,077, in 909; Reference the 6th hurdle the 13rd walks to the 7th hurdle the 62nd row and the 9th hurdle the 10th walks to the 10th hurdle the 11st row.Illustrate that hot in nature or direct alkylation method relates to usually under an inert atmosphere polyolefine and maleic anhydride to be heated at 180-250 DEG C.Often kind of reactant can be excessive.If the excessive existence of maleic anhydride, then this excessive can after the reaction by distillation removing.These reactions can use high vinylidene polyisobutylenes as polyolefine, and namely high vinylidene polyisobutylenes has the terminal vinylidene being greater than 50,70 or 75%, in some embodiments, and the sub-vinylic end group of α.In certain embodiments, succinimide dispersants is prepared by direct alkylation route.In other embodiments, it can comprise the mixture of direct alkylation and chlorine route dispersion agent.

Can by any one in these additives with any one aftertreatment in plurality of reagents to give its desired properties.This kind of aftertreatment comprises with urea, thiocarbamide, dimercaptothiodiazole, dithiocarbonic anhydride, aldehyde, ketone, carboxylic acid, hydrocarbon substituted succinyl oxide, nitrile, epoxide, boron compound as boric acid, phosphorus compound or its mixture reaction.The reference that this kind of process is described in detail in detail lists in United States Patent (USP) 4,654, in 403.

Other suitable alkyl replaces nitrogenous additive and comprises acylated amine, alkyl replacement amine or its mixture.

Suitable acylated amine comprises the reaction product of one or more carboxylic acid acylating agents and one or more amine.Carboxylic acid acylating agent comprises C _8-30lipid acid, C _14-20different aliphatic acid, C _18-44dimeracid, addition dicarboxylic acid, trimer acid, addition tricarboxylic acid and hydrocarbyl replaces carboxylic acid's acylating agent, comprise above-mentioned those.Dimeracid is described in United States Patent(USP) Nos. 2, and 482,760,2,482,761,2,731,481,2,793,219,2,964,545,2,978,468,3,157,681 and 3,256, in 304.Suitable amine can be above-mentioned any one in those, in some embodiments, be polyamines, such as alkylene polyamine or condensation polyamines.Acylated amine, their intermediate and preparation method thereof are described in United States Patent(USP) Nos. 3,219,666; 4,234,435; 4,952,328; 4,938,881; 4,957,649; 4,904,401; With 5,053, in 152.

Alkyl replaces nitrogenous additive can also replace amine for alkyl.It is well known to those skilled in the art that these alkyl replace amine.These amine are described in United States Patent(USP) Nos. 3, and 275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433; With 3,822, in 289.Usually, alkyl replaces amine by making alkene and olefin polymer, comprises said polyolefins and halide derivative thereof, reacts with amine (monoamine or polyamines) and prepare.Amine can be any one in amine described herein, in some embodiments, is alkylene polyamine.

The example that alkyl replaces amine comprises ethylene, such as diethylenetriamine; Poly-(propylidene) amine; N, N-dimethyl-N-gathers (ethylidene/propylidene) amine (50:50 monomer mole ratio); Polybutene amine; N, N-bis-(hydroxyethyl)-N-polybutene amine; N-(2-hydroxypropyl)-N-polybutene amine; N-polybutene-aniline; N-polybutene morpholine; N-gathers (butylene) quadrol; N-gathers (propylene) trimethylene diamine; N-gathers (butylene) diethylenetriamine; N', N'-gather (butylene) tetren; N, N-dimethyl-N'-poly-(propylene)-1,3-propylene diamine etc.

In some embodiments, above-mentioned alkyl is replaced nitrogenous additive boration.Can by any one boration in additive described herein, usually by making additive and boron-containing compound prepare as acid reaction.

In one embodiment, boron compound is borated dispersants.Usually, borated dispersants comprises about 0.1% to about 5%, or about 0.5% to about 4%, or the boron of 0.7% to about 3 % by weight.In one embodiment, borated dispersants is boration acylated amine, such as boration succinimide dispersants.Borated dispersants is described in United States Patent(USP) Nos. 3, and 000,916; 3,087,936; 3,254,025; 3,282,955; 3,313,727; 3,491,025; 3,533,945; 3,666,662 and 4,925, in 983.In one embodiment, boron compound is alkali or mixed alkali metal and alkaline earth metal borate.These metal borates are generally hydrated particles metal borate as known in the art.Alkali metal borate comprises mixed base and basic metal borate.These metal borates are commercially available.The Exemplary patents of open appropriate base and alkali and alkaline earth metal ions borate and production method thereof comprises United States Patent(USP) Nos. 3,997,454; 3,819,521; 3,853,772; 3,907,601; 3,997,454; With 4,089,790.

Also above-mentioned alkyl can be replaced nitrogenous additive by the aftertreatment with any one reaction in the plurality of reagents except boric acid agent.Wherein, these are urea, thiocarbamide, dimercaptothiodiazole, dithiocarbonic anhydride, aldehyde, ketone, carboxylic acid, Hydrocarbyl-substituted succinic acid anhydrides, nitrile, epoxide and phosphorus compound.The reference that this process is described in detail in detail lists in United States Patent (USP) 4,654, in 403.

The amine replacing nitrogenous additive for the preparation of above-mentioned alkyl can be polyamines.Suitable polyamines comprises aliphatic series, alicyclic, heterocycle and aromatic polyamine.The example of polyamines comprises alkylene polyamine, hydroxyl polyamines, aryl polyamines and heterocyclic polyamines.

Alkylene polyamine is expressed from the next:

(H) (R ₅) N-(alkylidene group-N) _n-(R ₅) (R ₅)

Wherein n has 1, or about 2 to about 10, or to about 7, or to about 5 mean value, and " alkylidene group " has 1, or about 2 to about 10, or to about 6, or to about 4 carbon atoms.R ₅be hydrogen independently of one another, or there is the aliphatic series of about 30 carbon atoms at the most or the aliphatic group of hydroxyl replacement.

Suitable alkylene polyamine comprises methylene radical polyamines, ethylene, butylidene polyamines, propylidene polyamines, pentylidene polyamines etc.Also can comprise higher homologue and related heterocycles amine, the piperazine that such as piperazine and N-aminoalkyl group replace.The specific examples of this kind of polyamines is quadrol, diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), three-(2-aminoethyl) amine, propylene diamine, trimethylene diamine, tri propylidene tetramine, tetren, six ethylidene seven amine, penten etc.

Use by two or more in above-mentioned alkylene amines similarly, as the mixture condensation of two or more in above-mentioned polyamines and the higher homologue obtained.

Ethylene, such as above-mentioned those are useful.This kind of polyamines is described in detail in " the Encyclopedia of Chemical Technology " of Kirk Othmer, 2nd edition, the 7th volume, 22-37 page, under title ethyleneamines in Interscience Publishers, New York (l965).This kind of polyamines is most conveniently by Ethylene Dichloride and ammonia react or reacted as water, ammonia etc. by ethylene imine and Ring Opening Reagent and prepared.These reactions cause the complex mixture producing polyalkylene polyamine, comprise cyclic condensation product as above-mentioned piperazine.Ethylene mixture is also useful.

The useful polyamine mixture of other type for above-mentioned polyamine mixture stripping is commonly referred to stay " polyamines still is residual " residue and produce those.Generally speaking, alkylene polyamine still is residual to be characterized by have and to be less than 2%, is usually less than the material of the boiling below about 200 DEG C of 1% (weighing scale).By Dow Chemical Company of Freeport, the residual representative instance of this kind of ethylene still that what Texas obtained be appointed as " E-100 " has the proportion of at 15.6 DEG C 1.0168, % by weight nitrogen of 33.15 and the viscosity of 121 centistokes at 40 DEG C.The gas chromatographic analysis of this sample comprises about 0.93% " lighting end " (most likely DETA), 0.72%TETA, 21.74% tetren and 76.61% penten and higher (weighing scale).These alkylene polyamine stills are residual comprises cyclic condensation product, the higher homologue of such as piperazine and diethylenetriamine, Triethylenetetramine (TETA) etc.These alkylene polyamine stills are residual can only can be used with acylation reaction or they together with other amine, polyamines or its mixture.

Another useful polyamines be at least one oxy-compound and at least one comprise at least one uncle or secondary amino group polyamine reactant between condensation reaction.In some embodiments, oxy-compound is polynary alkohol and amine.Polyvalent alcohol is above-mentioned.In some embodiments, oxy-compound is polyhydroxy amine.Polyhydroxy amine comprises and has 2 to about 20, or any one in the above-mentioned monoamine reacted to the oxyalkylene (such as ethylene oxide, propylene oxide, oxybutylene etc.) of about 4 carbon atoms.The example of polyhydroxy amine comprises three-(hydroxypropyl) amine, three-(methylol) aminomethanes, 2-amino-2-methyl-1, ammediol, N, N, N', N'-tetra-(2-hydroxypropyl) quadrol and N, N, N', N'-tetra-(2-hydroxyethyl) quadrol in some embodiments, is three (methylol) aminomethane (THAM).

In another embodiment, polyamines is hydroxyl polyamines.Also the hydroxyl polyamines homologue, particularly alkoxylate alkylene polyamine (such as N, N (di-alcohol) quadrol) of hydroxy monoamine can be used.This kind of polyamines reacts by one or more in above-mentioned alkylene polyamine and above-mentioned oxyalkylene and prepares.Also similar oxyalkylene-alkanolamine reaction product can be used, such as, by product that above-mentioned primary, secondary or tertiary alkanolamine and ethylene oxide, propylene oxide or senior epoxide are prepared with 1:1-1:2 molar ratio reaction.Reactant ratio and the temperature of carrying out this kind of reaction are well known by persons skilled in the art.

The specific examples of alkoxylate alkylene polyamine comprises N-(2-hydroxyethyl) quadrol, two (2-hydroxyethyl) quadrol of N, N-, 1-(2-hydroxyethyl) piperazine, list (hydroxypropyl) replace tetren, N-(3-hydroxyl butyl) four ethylene diamines etc.The higher homologue obtained by amino or hydroxyl condensation by above-mentioned hydroxyl polyamines is also useful.Producing higher amines by amino condensation, simultaneously except deammoniation, and being produced the product comprising ehter bond by hydroxyl condensation, simultaneously except anhydrating.In above-mentioned polyamines, two or more mixture any is also useful.

In another embodiment, amine is heterocyclic polyamines.Heterocyclic polyamines comprise aziridine, azetidine, azoles alkane, pyridine, pyrroles, indoles, piperidines, imidazoles, piperazine, isoindole, purine, morpholine, thiomorpholine, N-aminoalkylmorpholines, N-aminoalkyl group thiomorpholine, N-aminoalkyl piperazine, N, N'-Diaminoalkyl piperazine, azepines, azocine, azonine, a word used for translation ninth of the ten Heavenly Stems because of (azecine) and above-mentioned separately four-, two-and perhydro-derivative, and two or more mixture in these heterocyclic amines.In some embodiments, heterocyclic amine is saturated 5-and the 6 yuan heterocyclic amine only comprising nitrogen, oxygen and/or sulphur in heterocycle, especially piperidines, piperazine, thiomorpholine, morpholine, tetramethyleneimine etc.The tetramethyleneimine that the morpholine that the piperazine that the piperidines that piperidines, aminoalkyl group replace, piperazine, aminoalkyl group replace, morpholine, aminoalkyl group replace, tetramethyleneimine and aminoalkyl group replace.Usually, aminoalkyl substituent group is substituted on the nitrogen-atoms of a part forming heterocycle.The specific examples of this kind of heterocyclic amine comprises APM, N-aminoethyl piperazine and N, N'-diamino ethyl piperazine.Hydroxyl heterocyclic polyamines is also useful.Example comprises N-(2-hydroxyethyl) hexahydroaniline, 3-hydroxycyclopent amine, p-hydroxyanilines, N-hydroxyethylpiperazin etc.

The amine replaced in nitrogenous additive for the preparation of above-mentioned alkyl also can for having at least 4 aromatic groups, at least one-NH ₂the amine of functional group and at least 2 second month in a season or tertiary amino.

There is at least 3 aromatic groups, at least one-NH ₂the suitable amine of functional group and at least 2 second month in a season or tertiary amino can be expressed from the next:

Wherein each variable can independently as hereafter define: R ¹can be hydrogen or C _1-5alkyl (usual hydrogen); R ²can be hydrogen or C _1-5alkyl (usual hydrogen); U can be aliphatic, alicyclic or aromatic group, and condition is when U is for aliphatic series, and aliphatic group can be containing 1-5, or the linear or sub-branched alkyl of 1-2 carbon atom; And w can be 1-10, or 1-4, or 1-2 (usual 1).

As selection, amine also can be expressed from the next:

Wherein each variable U, R ¹and R ²identical with above-mentioned, and w is 0-9 or 0-3 or 0-1 (usual 0).

The example with the suitable amine of at least 3 aromatic groups can be represented by any one in following formula:

In one embodiment, the amine with at least 3 aromatic groups can comprise the mixture of the compound that above-mentioned formula represents.Those skilled in the art are to be understood that these compounds also can with hereinafter described aldehyde reaction to form acridine derivatives.Except this compounds, those skilled in the art it should also be understood that other acridine structure also can be possible, and wherein aldehyde reacts with other benzyl of >NH group bridging.In the aromatic ring of N-bridging any one or all can both this kind of further condensation and may aromizing.

The example with the suitable amine of at least 3 aromatic groups can be two [p-(p-amino-benzene amido) phenyl]-methane, 2-(7-Amino-acridina-2-ylmethyl)-N-4-{4-[4-(4-Amino-phenylamino)-benzyl]-phenyl }-benzene-Isosorbide-5-Nitrae-diamines, N ⁴-{ 4-[4-(4-Amino-phenylamino)-benzyl]-phenyl }-2-[4-(4-Amino-phenylamino)-hexamethylene-1,5-dialkylene methyl]-benzene-1,4-diamines, N-[4-(7-Amino-acridina-2-ylmethyl)-phenyl]-benzene-Isosorbide-5-Nitrae-diamines or its mixture.

In one embodiment, the amine with at least 3 aromatic groups can be two [p-(p-amino-benzene amido) phenyl]-methane, 2-(7-Amino-acridina-2-ylmethyl)-N-4-{4-[4-(4-Amino-phenylamino)-benzyl]-phenyl }-benzene-Isosorbide-5-Nitrae-diamines or its mixture.

The amine with at least 3 aromatic groups is prepared by comprising the method making aldehyde and amine (usual 4-ADPA) react.Gained amine can be described as has at least 3 aromatic groups, at least one-NH ₂the alkylidene group coupling amine of functional group and at least 2 second month in a season or tertiary amino.

In some embodiments, alkyl replaces nitrogenous additive is succinimide dispersants.In some embodiments, alkyl replaces nitrogenous additive is non-boration succinimide dispersants.In some embodiments, succinimide dispersants is derived from alkylarylamine, polyethylene polyamine or its some combinations.In some embodiments; the succinyl oxide that succinimide dispersants replaces derived from alkyl or acid (its reactive equivalent; such as ester, acyl halide etc.); it is 500-3000 that the succinyl oxide that wherein alkyl replaces comprises molecular weight; or 1600-3000, or the polyisobutylene group of 1000-2000.

Suitable alkyl replaces nitrogenous additive and also comprises quaternary ammonium salt, also referred to as quaternary ammonium salt purification agent and/or dispersion agent.The example of suitable quaternary ammonium salt comprises (i) imide quaternary ammonium salt, (ii) Mannich quaternaries, (iii) the amine quaternary ammonium salt of polyalkylene replacement, (iv) amidoquat salt, (v) ester quat, (vi) polyester quaternary ammonium salt, or (vii) its any combination.

These all kinds of quaternary ammonium salts can be prepared in a variety of ways, but are usually reacted by on-quaternised nitrogenous compound and quaternizing agent and prepared.Use different on-quaternised nitrogenous compounds in its preparation of each leisure of described dissimilar quaternary ammonium salt, but usually on-quaternised nitrogenous compound comprise can quaternised tertiary nitrogen (or can be alkylated into the uncle of tertiary nitrogen (it then can be quaternized) or secondary nitrogen-atoms) and hydrocarbyl substituent.Usually this, as purification agent and/or dispersion agent, can provide the performance of improvement to on-quaternised compound when changing into quaternary ammonium salt.

Quaternary ammonium salt purification agent and/or dispersion agent, and/or the hydrocarbyl substituent of the on-quaternised nitrogenous compound preparing them is unduly limited, and can be any one in the hydrocarbyl substituent herein derived.

Above-mentioned quaternary ammonium salt uses quaternizing agent to prepare separately.Suitable quaternizing agent is unduly limited, and condition is that the tertiary nitrogen transformation of on-quaternised precursor can be become quaternary nitrogen by them.Suitable quaternizing agent comprises dialkyl sulfate, benzyl halide, alkyl replace carbonic ether, hydrocarbyl epoxides, the ester of some poly carboxylic acid or its mixture.Any one in these reagent, comprises hydrocarbyl epoxides and alkyl replaces carbonic ether, can use with acid such as acetic acid combinations.Suitable acid comprises carboxylic acid, such as acetic acid, propionic acid, 2 ethyl hexanoic acid etc.In some embodiments, comprise such as amidoquat salt, quaternizing agent, comprise hydrocarbyl epoxides and alkyl and replace carbonic ether not adding under this kind of acid and use.In some embodiments, particularly when not using acid, during reaction there is the water of a tittle.

In some embodiments, quaternizing agent can be hydrocarbyl epoxides, is shown below:

Wherein R ¹⁵, R ¹⁶, R ¹⁷and R ¹⁸can be H or C independently _1-50alkyl.The example of suitable hydrocarbons based epoxy comprises: Styrene oxide 98min., ethylene oxide, propylene oxide, oxybutylene, oxidation stilbene, C _2-50epoxide or its combination.

About above-mentioned amidoquat salt, the existence of amide group and allow that salt is " from salinization " to the impact of structure rest part, therefore do not need negatively charged ion separately, wherein putative structure also comprises at least one other acid groups.Such as, when Hydrocarbyl-substituted succinic acid anhydrides and analogous material are for the preparation of on-quaternised nitrogenous compound, gained quaternary ammonium salt can have amide group and acid groups, and wherein acid groups becomes the counter anion of quaternary nitrogen or gained amidoquat salt.These materials can be described as trimethyl-glycine.The feature of the preparation of these quaternary ammonium salts typically uses oxyalkylene quaternizing agent or similar reagents and does not add acid separately.

In another embodiment, quaternizing agent can be the ester of carboxylic acid or the ester of poly carboxylic acid.In some embodiments, quaternizing agent comprises dimethyl oxalate, 2-nitrobenzene methyl and wintergreen oil.

In some embodiments; quaternary ammonium salt is by making alkyl replace acylating agent and having the condensation product polymerization that can acidylate the oxygen of agent condensation or the compound of nitrogen-atoms; wherein condensation product has at least one uncle's amino; or even make alkyl replace acylating agent polymerization, then react with the compound with oxygen or nitrogen-atoms and the quaternary ammonium polymer that formed.One or more methods described herein that then can use in tertiary amino on polymkeric substance are quaternized, produce quaternary ammonium polymer.

Any one in above-mentioned quaternary ammonium salt can obtain under the existence of protonic solvent.In some embodiments, the method for the preparation of these additives substantially contains to not containing methyl alcohol.In one embodiment, protonic solvent comprises the compound containing one or more hydroxy functional group, and can comprise water.In some embodiments, protonic solvent is water.

Other details about quaternary ammonium salt, the example and preparation method thereof can at United States Patent (USP) 7,951,211 and 7,906,470, US openly applies for finding in US 2008/0113890, US 2012/0010112 and US2011/0315107 and International Publication WO 2010/132259, WO 2010/097624 and WO2011/095819.

Nitrogenous dispersion agent can be polyetheramine.In some embodiments, polyetheramine can comprise the compound with two or more continuous ether groups and at least one primary, secondary or tertiary amine groups, and wherein ammonia nitrogen has some basicity.Polyetheramine of the present invention can comprise poly-(oxyalkylene) amine, and described poly-(oxyalkylene) amine has enough repeated oxidation alkene number of unit and dissolves in normal liquid fuel as in the mixture of the hydrocarbon of boiling point in gasoline or diesel fuel range and hydrocarbon fuel and nonhydrocarbon fuel to make to gather (oxyalkylene) amine.Generally speaking, poly-(oxyalkylene) amine with at least 5 oxyalkylene units is applicable in the present invention.

Poly-(oxyalkylene) amine can comprise: alkyl gathers (oxyalkylene) amine, poly-(oxyalkylene) polyamines of alkyl, poly-(oxyalkylene) amine of hydrogenation, poly-(oxyalkylene) polyamines of hydrogenation, and derivative molecular has the polyol derivative of at least 2 poly-(oxyalkylene) amine and/or poly-(oxyalkylene) polyamines chain.

In one embodiment, be expressed from the next for poly-(oxyalkylene) amine in the present invention:

R ⁶O(A ²O) _mR ⁷NR ⁸R ⁹

Wherein R ⁶for having the alkyl of 1-50 carbon atom or 8-30 carbon atom; A ²for having 2-18 carbon atom, the alkylidene group of 2-6 carbon atom in some embodiments; M is the number of 1-50; R ⁷for having the alkylidene group of 2-18 carbon atom or 2-6 carbon atom in some embodiments; And R ⁸and R ⁹be hydrogen, alkyl or-[R'N (R ")] nR independently " ', wherein R' is the alkylidene group with 2-6 carbon atom, and R " and R " ' is hydrogen or alkyl independently, and n is the number of 1-7.

In another embodiment, poly-(oxyalkylene) amine of the present invention can be expressed from the next:

R ¹⁰O[CH ₂CH(CH ₂CH ₃)O] _ZCH ₂CH ₂CH ₂NH ₂

Wherein R ¹⁰for the phenyl that the aliphatic group or alkyl with 8-30 carbon atom replace; And Z is the number of 12-30.In yet another embodiment, poly-(oxyalkylene) amine of the present invention can be represented by above formula, wherein R ¹⁰for CH ₃cH (CH ₃) [CH ₂cH (CH ₃)] ₂cH (CH ₃) CH ₂cH ₂-, and Z is the number of 16-28.Poly-(oxyalkylene) amine of the present invention can have 300-5, the molecular weight of 000.

Polyetheramine of the present invention is by using above-mentioned polyethers as intermediate and they being changed into polyetheramine and prepares.Polyether intermediate changes into polyetheramine by several method.Polyether intermediate by changing into polyetheramine with ammonia, primary amine or polyamines reduction amination, as United States Patent(USP) Nos. 5,112,364 and 5,752, described in 991.In one embodiment, hydrogenating nitriles by the addition reaction of polyethers on vinyl cyanide to form nitrile, then can be changed into polyetheramine to form polyetheramine by polyether intermediate.U.S. Patent No. 5,264,006 provides polyethers vinyl cyanide cyanoethylation, and hydrogenation subsequently forms the reaction conditions of polyetheramine.In yet another embodiment, chlorine ammonia, uncle or secondary amine or polyamines, by suitable chlorizating agent, replace thereafter and change into corresponding poly-(oxyalkylene) muriate, as U.S. Patent No. 4 by polyether intermediate or poly-(oxyalkylene) alcohol, 247, described in 301.

Mixed oxyalkyl compound of the present invention also can comprise alkoxylated fats amine, and described alkoxylated fats amine can comprise the amine that following formula represents:

Wherein R ¹¹for there is the alkyl of 4-30 carbon atom, A ³and A ⁴for contiguous alkylidene group, and x's and y and be at least 1 integer.Alkyl is the monoradical with carbon atom, and it is being mainly hydrocarbon in nature, but can have substituents and can have heteroatoms.Alkyl R ¹¹can for having 4-30 carbon atom, or the alkyl of 10-22 carbon atom or alkylidene group.Contiguous alkylene group A ³and A ⁴can be identical or different, and comprise: ethylidene (-CH ₂-), propylidene (-CH ₂cH ₂cH ₂-) and butylidene (-CH ₂cH ₂cH ₂cH ₂-), wherein vicinity or adjacent carbons have carbon-nitrogen and carbon-oxygen bond.The example of alkoxylated fats amine can comprise: diethoxy tallow amine, diethoxy carburetion amine, diethoxy stearylamine and the diethoxy amine from soya fatty acid.Alkoxylated fats amine with series is commercial by Akzo.

Nitrogenous compound can with the 0.01-5 % by weight of described composition, or 0.1-3 % by weight, or 0.2-1.5 % by weight, or 0.25-1 % by weight, or 0.5-1 % by weight exists.

sulfocompound

In some embodiments, bearing lubricant of the present invention or use their method also can comprise (d) sulfocompound.

Suitable sulfocompound comprises olefine sulfide.Any alkene described about other component herein is also the suitable alkene can preparing olefine sulfide.In some instances, sulfocompound is derived from iso-butylene, butylene, propylene, ethene or its some olefine sulfides combined.In some instances, sulfocompound be derived from above-mentioned natural oil or synthetic oil any one, or olefine sulfides of even its some combination.Such as, olefine sulfide can derived from vegetables oil.

When it is present, sulfocompound can with the 0.01-5 % by weight of described composition, or 0.1-3 % by weight, or 0.2-1.5 % by weight, or 0.25-1 % by weight, or 0.5-1 % by weight exists.

other additive

Optionally, lubricating composition of the present invention comprises one or more other additives, and other additive described can be selected from the group comprising following additive: suds suppressor, demulsifying compound, pour point reducer, antioxidant, be different from above-mentioned those dispersion agent, metal passivator (such as copper passivator), be different from above-mentioned those anti-wear agent, extreme pressure agent, viscosity modifier or its mixture.Optional additives can separately with 50,75,100 or even 150ppm to 5,4,3,2 or even 1.5 % by weight, or 75ppm to 0.5 % by weight, 100ppm to 0.4 % by weight, or the scope of 150ppm to 0.3 % by weight exists, and wherein % by weight value is about total lubricating oil composition.But should be understood that when considering to separate with basic fluid, some optional additives, comprising the viscosity modified polymkeric substance that can be used as and select to be considered to a part for basic fluid, the higher amount that can comprise at the most 30,40 or even 50 % by weight exists.Optional additives can use separately or with its mixture.

Defoamer also referred to as suds suppressor is as known in the art, includes but not limited to organo-siloxane and non-silicon suds suppressor.The example of organo-siloxane comprises dimethyl siloxane and polysiloxane.The example of non-silicon suds suppressor includes but not limited to the multipolymer of polyethers, polyacrylic ester and composition thereof and ethyl acetate, 2-ethylhexyl acetate and optional vinyl-acetic ester.In some embodiments, defoamer is polyacrylic ester.Defoamer can with 0.001 to 0.012 or 0.004pbw or even 0.001-0.003 be present in composition.

Demulsifying compound is as known in the art, includes but not limited to the derivative of propylene oxide, ethylene oxide, polyoxygenated enol, alkylamine, amino alcohol, with ethylene oxide or replace the diamines or polyamines that ethylene oxide or its mixture sequentially react.The example of demulsifying compound comprises polyoxyethylene glycol, polyoxyethylene, polyoxytrimethylene, (ethylene oxide-propylene oxide) polymkeric substance and composition thereof.In some embodiments, demulsifying compound is polyethers.Demulsifying compound can be present in composition with 0.002-0.012pbw.

Pour point reducer is as known in the art, includes but not limited to the ester of maleic anhydride-styrene copolymers, polymethacrylate; Polyacrylic ester; Polyacrylamide; The condensation product of halogenated paraffins and aromatic substance; Carboxylic acid vinyl ester polymer; And the trimer of dialkyl fumarate, lipid acid vinyl acetate, vinyl-vinyl acetate copolymer, alkyl phenol formaldehyde condensation resins, alkyl vinyl ether and composition thereof.

The present composition also can comprise the rust-preventive agent being different from some above-mentioned additives.Suitable rust-preventive agent comprises the alkyl amine salt of dialkyl dithiophosphoric acid, the alkyl amine salt of alkyl arene-sulfonic acids, aliphatic carboxylic acid or its ester, ester, ammonium sulphonate, tetrahydroglyoxaline, single thiophosphate salt or ester containing nitronic acid, or its any combination; Or its mixture.

The example of the alkyl amine salt of dialkyl dithiophosphoric acid of the present invention include but not limited to above-mentioned those, and the reaction product of diheptyl or dioctyl or dinonyl phosphorodithioic acid and quadrol, morpholine or Primene81R, or its mixture.Alkyl amine salt for the suitable alkyl arene-sulfonic acids in rust-preventive agent bag of the present invention is expressed from the next:

Wherein Cy is benzene or naphthalene nucleus.R ²⁸for having about 4 to about 30, preferably about 6 to about 25, the more preferably from about alkyl of 8 to about 20 carbon atoms.Z is 1,2,3 or 4 independently, and most preferably z is 1 or 2.R ²³, R ²⁴and R ²⁵as described above.

The example of the alkyl amine salt of alkyl arene-sulfonic acids of the present invention includes but not limited to the ethylenediamine salt of dinonylnaphthalene sulfonic acid.

The example of suitable fat carboxylic acid or its ester comprises XU 61518.10 and oleic acid.The example of the suitable ester containing nitronic acid comprises oleoyl sarcosine.

Rust-preventive agent can with the 0.02-0.2 of lubricating oil composition, 0.03 to 0.15,0.04-0.12, or 0.05-0.1pbw exists.Rust-preventive agent of the present invention can use separately or with its mixture.

Lubricating composition of the present invention also can comprise metal passivator.The catalytic effect of the oxidation during metal passivator is used for and in metal promoted lubricating oil.Suitable metal passivator includes but not limited to triazole, tolyl-triazole, thiazole or its combination, and its derivative.Example comprises and is different from those benzotriazole derivatives, benzoglyoxaline, 2-alkyl dithio benzoglyoxaline, 2-alkyl dithio benzothiazole, 2-(N above-mentioned; N '-dialkyl dithio-formamyl) benzothiazole, 2; two (alkyl-dithio)-1 of 5-; 3; 4-thiadiazoles, 2,5-two (N, N '-dialkyldithiocarbamoyl)-1; 3,4-thiadiazoles, 2-alkyl dithio-5-dimercaptothiodiazole or its mixture.These additives can with 0.01-0.25 % by weight in total composition.

In some embodiments, metal passivator is the benzotriazole cpd that alkyl replaces.There is the benzotriazole cpd that alkyl replaces and comprise at least one in following ring position 1-or 2-or 4-or 5-or 6-or 7-benzotriazole.Alkyl comprises about 1 to about 30, and preferably about 1 to about 15, more preferably from about 1 to about 7 carbon atom, most preferred metal passivator is the 5-Methylbenzotriazole or its mixture that are used alone.

Metal passivator can exist with 0.001-0.1,0.01-0.04 or 0.015-0.03pbw of lubricating oil composition.Metal passivator also can be present in composition with 0.002 or 0.004 to 0.02pbw.Metal passivator can use separately or with its mixture.

Also can there is antioxidant, comprise (i) alkylated diphenylamine and (ii) substituted hydrocarbon radical list sulfide.In some embodiments, alkylated diphenylamine of the present invention is two nonylated diphenylamine and two octylated diphenylamine.In some embodiments, substituted hydrocarbon radical list sulfide comprises dodecyl-2-hydroxyethyl sulfide, 1-(uncle-dodecylthio)-2-propyl alcohol or its combination.In some embodiments, substituted hydrocarbon radical list sulfide is 1-(uncle-dodecylthio)-2-propyl alcohol.

Antioxidant bag also can comprise sterically hindered phenol.The example of suitable alkyl includes but not limited to 2-ethylhexyl or n-butyl, dodecyl or its mixture.The example of methylene-bridged sterically hindered phenol includes but not limited to 4,4 '-methylene radical-bis-(6-butyl o-cresol), 4,4 '-methylene radical-bis-(2-tert-pentyl-ortho-cresol), 2,2 '-methylene radical-bis-(4-methyl-6-tert-butyl phenol), 4,4 '-methylene radical-bis-(2,6-, bis--tertiary butyl phenol) or its mixture.

In some embodiments, the present composition does not contain substantially, or even completely containing alkylated phenol, alkarylamine or the two, or comprise no more than 2.0 % by weight, 1.0 % by weight, or even 0.5 % by weight they, wherein % by weight value refers to be present in the total amount of alkylated phenol in total lubricant and/or alkarylamine.

Embodiment

Set forth the present invention further by following examples, described embodiment describes particularly advantageous embodiment.Although provide embodiment to set forth the present invention, they are not intended to limit it.

embodiment group 1

Prepare one group of coal pulverizer lubricant compositions embodiment.The preparation of embodiment is summarized in following table with % by weight, and wherein P contained compound and nitrogenous dispersion agent are listed based on active substance.

Table 1

The basic medium of 1-is the mixture of polyalphaolefin (group IV) base oil and polyisobutylene base oil.Unless otherwise noted, identical basic medium is used in each embodiment, and is present in each embodiment with identical amount based on PBW.With regard to each embodiment, the difference of list % by weight is only the difference amount due to P contained compound and nitrogenous dispersion agent in each embodiment.

P contained compound in 2-embodiment is alkenyl phosphite.

Nitrogenous dispersion agent in 3-embodiment is succinimide dispersants.

Other additive-package that 4-is identical is used for each embodiment, and is present in each embodiment with identical amount based on PBW.With regard to each embodiment, the difference of list % by weight is only the difference amount due to P contained compound and nitrogenous dispersion agent in each embodiment.

5-embodiment 9 is sell the commercially available lubricant being used for this application.The preparation of this lubricant is unknown, so this material is only included as the example of the commercially available traditional lubrication agent for this application.

At simulation pulverizer, in the program of the severe condition seen in the bearing of specifically coal pulverizer, test each embodiment lubricant.Coal dust added the pollution that occurs with simulated field in embodiment lubricant and measure the impact of lubricant properties to prove the ability that embodiment provides acceptable performance under those circumstances.Test uses high-load KRL type trier and SNR 32008.C test bearing.Testing sequence relates to following steps:

(1) new test bearing is cleaned 15 minutes with toluene in ultra sonic bath.Make bearing drying with fabric alcohol rinse.

(2) when obtaining on-test, bearing weight is to decimilligram.

(3) bearing is placed in the test head of KRL type trier.

(4) 0.9 % by weight coal dust is added in embodiment lubricant.Use vibration at high speed machine by lubricant and coal dust well blend, then the embodiment lubricant of the powder contamination of test head 30ml is filled.

(5) test head is arranged in KRL type trier.

(6) test conditions listed by table 2, it is designed for the severe condition and operator scheme that experience in the bearing of simulation pulverizer:

Table 2

Stage	Speed (rpm)	Load (kg)	Temperature (DEG C)	Time (hour)
					Trial trip	150	800	90	1
Trial trip	300	800	90	1
					Trial trip	430	800	90	2
Trial trip	150	1600	90	1
					Trial trip	300	1600	90	1
Trial trip	430	1600	90	2
					Trial trip	150	2400	90	1
Trial trip	300	2400	90	1
					Test	430	2400	90	48

(1) when off-test, take out, preserve and mark embodiment lubricant.

(2) by the washing test bearing with fabric alcohol rinse, then bearing is cleaned 15 minutes with toluene in ultra sonic bath.Again with fabric alcohol rinse, and make bearing drying.

(3) when obtaining off-test, bearing weight is to decimilligram.

(4) by on-test and at the end of weight determination weight loss, and the wear metal amount of embodiment lubricant at the end of analytical test.

Test-results from embodiment lubricant is summarized in following table:

Table 3

1-, for total weight loss, is worth lower, and the performance of lubricant is better.With regard to assessment lubricant properties, total weight loss is the more important results presented above.

2-is the mean value of twice test-results about the result that embodiment 7 shows.

3-is the mean value of three test-results about the result that embodiment 8 shows.

4-is the mean value of four test-results about the result that embodiment 9 shows.

Result shows pulverizer bearing lubricant of the present invention and uses its method can provide significant performance under pulverizer bearing finding severe condition.Described lubricant and method are particularly advantageous compared with the existing commercially available selection of applying for these.

embodiment group 2

Do not prepare second group of coal pulverizer lubricant compositions embodiment with adding other additive any.The preparation of embodiment is summarized in following table with % by weight, and wherein P contained compound and nitrogenous dispersion agent are listed based on active substance.

Table 4

The basic medium of 1-is the mixture of polyalphaolefin (group IV) and polyisobutylene base oil.Unless otherwise noted, identical basic medium is used in each embodiment.Join the footnote 1 seen the above table in 1.

P contained compound in 2-embodiment is alkenyl phosphite.

Nitrogenous dispersion agent in 3-embodiment is succinimide dispersants.

Other additive does not add in these embodiments by 4-.

5-embodiment 10 is sell the commercially available lubricant being used for this application.The preparation of this lubricant is unknown, so this material is only included as the example of the commercially available traditional lubrication agent for this application.Embodiment 11 is identical commercially available lubricant, but now with additive combination pre-treatment of the present invention (top treat).

With the embodiment of above-mentioned identical test program evaluates table 4.The results are summarized in following table:

Table 5

2-is the mean value of three test-results about the result that embodiment 10 shows.

3-is the mean value of four test-results about the result that embodiment 11 shows.

Especially, should be understood that the embodiment of the present invention (embodiment 13,14,15 and 18) all has than routine and do not add lubricant (embodiment 10 and 12) better weight loss results.Embodiment 16 has good weight loss results, but the amount of iron during off-test in lubricant is extremely high.Equally, embodiment 17 has rationally, but still high iron, but has high weight loss.On the contrary, the embodiment of the present invention obtains the well balanced of result both ways.In addition, the commercial embodiment (embodiment 12) of pre-treatment also demonstrates significant improvement when applying the present invention to it.

At this, above-mentioned each file is incorporated to the present invention by reference.Except in embodiment, or outside clearly stating in addition, all quantity of description amount in this manual, reaction conditions, molecular weight, carbonatoms etc. are to be understood that is modified by wording " about ".Except as otherwise noted, all percentage ratio and preparation value are all based on weight.Except as otherwise noted, all molecular weight are weight-average molecular weight.Except as otherwise noted, each chemical mentioned herein or composition should be understood to the commercial grade material that can contain isomer, by product, derivative and usually be to be understood that other this kind of material be present in commercial grade.But except as otherwise noted, the amount of each chemical composition is expressed as to eliminate and usually can be present in any solvent in commercial materials or thinner.Be to be understood that the upper and lower bound of amount described herein, scope and ratio can combine independently.Similarly, the scope of each element of the present invention can use with the scope of other element any or together with measuring with amount.As used herein, statement " substantially by ... composition " allows to comprise and does not affect the essential characteristic of composition considered and the material of new feature in essence.

Claims

1. the method for the bearing of lubricating solid fuel pulverizer, it comprises step:

I. in described bearing, feed the lubricant compositions comprising following component:

A () has the oil of lubricant viscosity;

(b) P contained compound; With

(c) nitrogenous dispersion agent;

And wherein lubricant compositions optionally comprises further:

(d) sulfocompound.

2. method according to claim 1, the oil wherein with lubricant viscosity comprises mineral base oil.

3. method as claimed in one of claims 1-2, the oil wherein with lubricant viscosity comprises synthesis base oil.

4. method as claimed in one of claims 1-3, wherein P contained compound comprises alkyl phosphite, phosphoric acid ester, the amine salt of phosphoric acid ester or its some combinations.

5. method as claimed in one of claims 1-4, wherein nitrogenous dispersion agent comprises: polyetheramine; Boration succinimide dispersants; Non-boration succinimide dispersants; Comprise the Mannich dispersant of the reaction product of dialkylamine, aldehyde and alkyl fortified phenol; Or its any combination.

6. method as claimed in one of claims 1-5, wherein nitrogenous dispersion agent comprises the non-boration succinimide dispersants derived from aromatic amine.

7. method as claimed in one of claims 1-6, wherein lubricant compositions comprises further: (d) sulfocompound.

8. method as claimed in one of claims 1-8, wherein P contained compound comprises alkyl phosphite and nitrogenous dispersion agent comprises non-boration succinimide dispersants.

9. method as claimed in one of claims 1-9, wherein P contained compound is present in lubricant compositions with 0.01-5.0 % by weight; And

Wherein nitrogenous dispersion agent is present in lubricant compositions with 0.01-4.0 % by weight.

10., for the bearing lubricant of solid fuel pulverizer, it comprises:

A () has the oil of lubricant viscosity;

(b) P contained compound; With

(c) nitrogenous dispersion agent.

11. bearing lubricants according to claim 10, wherein P contained compound comprises alkyl phosphite, phosphoric acid ester, the amine salt of phosphoric acid ester or its some combinations.

12. bearing lubricants any one of claim 10-11, wherein nitrogenous dispersion agent comprises: polyetheramine; Boration succinimide dispersants; Non-boration succinimide dispersants; Comprise the Mannich dispersant of the reaction product of dialkylamine, aldehyde and alkyl fortified phenol; Or its any combination.

13. bearing lubricants any one of claim 10-12, wherein P contained compound is present in lubricant compositions with 0.01-5.0 % by weight; And

14. bearing lubricants any one of claim 10-13, wherein bearing lubricant comprises further: (d) sulfocompound.

15. lubricant compositions improve the work-ing life of solid fuel disintegrating apparatus centre bearer or the purposes of weather resistance, and described lubricant compositions comprises:

A () has the oil of lubricant viscosity;

(b) P contained compound; With

(c) nitrogenous dispersion agent.