CN105255528B - It is a kind of to prevent the compound additive of diesel antiwear additive spontaneous combustion - Google Patents
It is a kind of to prevent the compound additive of diesel antiwear additive spontaneous combustion Download PDFInfo
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- CN105255528B CN105255528B CN201510734002.8A CN201510734002A CN105255528B CN 105255528 B CN105255528 B CN 105255528B CN 201510734002 A CN201510734002 A CN 201510734002A CN 105255528 B CN105255528 B CN 105255528B
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Abstract
The invention belongs to unrighted acid or ester spontaneous combustion retardant technical field, specifically a kind of compound additive for preventing diesel antiwear additive in accumulating and filling link spontaneous combustion is formed by antioxidant, thermal conducting agent, dispersant and diluent compounding.The present invention is aoxidized by effectively suppressing unrighted acid or ester, promotes the means such as radiating to realize spontaneous combustion resistanceization effect.Volume of the additive of the present invention in diesel antiwear additive is low, and it is 1~2% to recommend volume, is Green Product without metal, halogen, phosphorus etc. to engine or environmentally hazardous substance.
Description
Technical field
The invention belongs to unrighted acid or ester spontaneous combustion retardant technology, specifically one kind prevents diesel antiwear additive
In the compound additive of accumulating and filling link spontaneous combustion, the security risk of petroleum and petrochemical industry production process can be effectively reduced.
Technical background
Diesel antiwear additive is divided to acid type and the class of ester type two, and acid type antiwear additive is typically to be answered by ready denier oil acid with other assistant agents
Match somebody with somebody and obtain, and ester type antiwear additive is then obtained by ready denier oil acid and polyhydric alcohol, both of which is based on ready denier oil acid
Want raw material.Ready denier oil acid is generally extracted from plant, main containing single unsaturated oleic acid, additionally containing a large amount of how unsaturateds
Linoleic acid plus linolenic acid, there is very big safety in these unrighted acids or the easily spontaneous combustion in atmosphere of its esterification products
Hidden danger, gives people to produce, lives and bring many inconvenience.
Spontaneous combustion is spontaneous combustion, ready denier oil acid or ester Linoleic acid (group) and leukotrienes caused by slow oxidation
(group) is easily oxidized because double bond is more, be located proximate to.And the progress of oxidation can further be promoted by aoxidizing the heat produced,
Single unsaturated oleic acid (group) that relative difficult is oxidized at normal temperatures is even triggered to aoxidize.Due to ready denier oil acid or
Ester viscosity is big, and the heat of generation can not disperse in time, once temperature exceedes ignition point, is easy for triggering spontaneous combustion.Such case exists
Ready denier oil acid or ester are particularly acute with (such as being wiped in the presence of dispersing morphology by rag), because it sticks to fabric
Upper rear oxidation contact area increase, and the fabric of rubbing is difficult to make the heat of generation to disperse event.
Industrially prevent ready denier oil acid or the method for ester spontaneous combustion from mainly having following two at present：1) isolation method, such as nitrogen
Envelope protection；2) fire retardant method, i.e., it is such as some to contain metal, halogen, phosphorus species to reduce tall oil fat by adding fire retardant
The spontaneous combustion tendency of fat acid or ester, conventional fire retardant has antimony oxide, PBDEs, PBBs etc..
Realized using blockading of nitrogen ready denier oil acid or ester spontaneous combustion by completely cutting off it with oxygen contact, of change
It is the physical environmental condition of fatty acid or ester, it is impossible to fundamentally solve the danger of fatty acid or ester spontaneous combustion.With disappearing for nitrogen
Consumption is lost in, and its flame retardant effect also fades away, therefore nitrogen envelope has the shortcomings of spontaneous combustion resistanceization decline phase is short, effect is poor.Relatively
For, fire retardant method is to be combined by the higher double bond of activity in chemically react destruction or reduction ready denier oil acid or ester with oxygen
To prevent its oxidation and spontaneous combustion, with irreversibility, thus flame retardant effect is better than nitrogen envelope.But, there is certain lack in fire retardant method
Fall into:1) fire retardant is usually to contain metal, halogen, phosphorus species, harmful to engine or environment；2) oxidation reaction process is to put
Thermal response, if the reaction heat of generation can not be removed in time, can still be raised and spontaneous combustion rapidly because of the temperature of fatty acid or ester.One
Individual common solution is ventilation and heat, but antiwear additive is typically sealing preserve, and this method is obviously unworkable.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, oxidizable and be difficult for ready denier oil acid or ester double bond
Dissipating thermal property, there is provided a kind of spontaneous combustion resistanceization compound additive based on unrighted acid oxidation and spontaneous combustion mechanism.The additive
Can effectively resistance ready denier oil acid or ester oxidation reaction chain, accelerate the heat release that oxidation is produced, inherently prevent appropriate
The spontaneous combustion of that fatty acid oil or ester.
The present invention realizes spontaneous combustion by changing formula rather than fatty acid or ester molecular structure, namely introducing third component
Resistanceization effect.Thus, the integrality of fatty acid or ester molecule will not be destroyed, and not interfere with its original antiwear characteristics.
The technical solution adopted in the present invention is:
It is a kind of to prevent the compound additive of diesel antiwear additive spontaneous combustion, compounded by antioxidant, thermal conducting agent, dispersant and diluent
Form, each component weight/mass percentage composition is：
Optimization formula is,
Described antioxidant is hindered phenol antioxygen, specifically to methyl 2,6- DI-tert-butylphenol compounds (BHT), β-
Double [3- (3,5- di-t-butyls-the 4- of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid isooctanol ester (antioxidant 1135), hexylene glycol
Hydroxy phenyl) propionic ester] (antioxidant 259), octadecyl 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic ester (antioxidant
1076), one kind of triethylene-glycol double [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester] (antioxidant 245) or
Several mixture, it is contemplated that antioxidant is with the intersolubility of antiwear additive, the present invention preferably antioxidant 1135,259 and 1076.
It is well known that some have flame retardant effect containing metal, halogen, phosphorus species.However, not having such one also so far
Fire retardant report is planted, i.e., it can effectively prevent ready denier oil acid or ester spontaneous combustion from meeting the strict environmental protection mark of oil dope again
It is accurate.Ready denier oil acid or ester spontaneous combustion process are an oxidative chain reactions processes, and some aldehydes matters can because of its phenolic hydroxyl group hydrogen
With radical reaction with antioxidant effect, ready denier oil acid or ester can be made not to aoxidize or aoxidize seldom, such temperature is obtained
Less than rise, being finally reached prevents the purpose of antiwear additive spontaneous combustion.
Described thermal conducting agent is Nano graphite powder, graphene or CNT, and Oil-soluble nano-graphite also can be used directly
Powder, graphene or CNT.Heat conductivility is an important indicator of spontaneous combustion retardant, if plus antiwear additive oxidation production after agent
Raw heat can quickly be lost to surrounding environment, so that it may suppress the generation of spontaneous combustion.The selection of heat conduction component should follow strict ring
Guaranteed request, Nano graphite powder, graphene or CNT are extensive as a kind of new material application, and are a kind of ashless, nontoxic nothings
Evil material, meets the indices requirement of oil dope.Therefore, from economic, environmental protection, efficiently from the point of view of, we select
Thermal conducting agent is used as using Nano graphite powder, graphene or CNT particularly Nano graphite powder.It is noted that graphite sheet
Body also has lubrication.
Described dispersant is unrighted acid (such as oleic acid, linoleic acid), span-80, pitch dispersant (such as asphalt mixtures modified by epoxy resin
Fat, terpene resin) in one or more of mixtures.Addition dispersant can reduce Nano graphite powder, graphene or carbon and receive
The surface tension of mitron, increases its oil-soluble, so that Nano graphite powder, graphene or carbon nanotube particulate divide in system
Dissipate uniform, heat conduction is more abundant.It is also a kind of diesel antiwear additive in itself to be because of oleic acid, span-80, the present invention preferably oleic acid, span-
80 are used as dispersant.
Described diluent is mixed trimethylbenzene, mixed durene, one or more of mixtures of heavy aromatics.
Described compound additive addition in Low sulfur diesel antiwear additive is 0.5~5%, preferably 1~2%.
The present invention has the following advantages:First, the compound retardant of the present invention is distributed in the heat for accelerating antiwear additive oxidation generation
On the basis of, the radical reaction that its antioxidant composition can be produced with oxidation prevents the progress of oxidation chain reaction, inherently
Change the oxidizable characteristic of antiwear additive, it is suppressed that its spontaneous combustion is inclined to；Secondly, of the invention the cost of material is low, without metal, halogen
Element, phosphorus etc., nonpoisonous and tasteless harmless, no environmental pollution is a kind of Green Product；Finally, volume of the invention is low, spontaneous combustion resistance
Change effect good, when addition is 1% in Low sulfur diesel antiwear additive, its heat generation starting temperature and spontaneous combustion Induction time have bright
It is aobvious to improve and increase.
Embodiment
The present invention is described in further detail by following examples, but the technology contents described in the present embodiment are illustrative, and
It is not limited, protection scope of the present invention should not be limited to according to this.
Embodiment 1
Sample preparation：
Antioxidant, thermal conducting agent, dispersant and diluent are weighed respectively, are sufficiently mixed and are produced the compound retardant of the present invention.Choosing
Commercially available acid type or ester type antiwear additive are taken, the compound retardant of preparation is proportionally added into, and is sufficiently mixed, as the present embodiment sample
Product.
Evaluation method：
1) TG-TDA (TG-DT A spectrum) is used to determine heat generation starting temperature when heating, the higher spontaneous combustion resistance rate of temperature
It is higher.Test condition：1. sample amount：10mg；2. heating rate：2℃/min；3. air mass flow：150mL/min.
2) SIT (spontaneous combustion test) is used to determine the time from heating to spontaneous combustion, and the time is longer, and spontaneous combustion resistance rate is higher.Test
Condition：1. sample amount：30mg；2. temperature：60℃；3. environment：Air.
The different component of table 1 compounds the influence to spontaneous combustion resistanceization effect
Note：1) constituent mass proportioning is antioxidant:Thermal conducting agent:Dispersant:Diluent=35：10：2：53；2) dosage is added
1%；3) experiment antiwear additive is certain commercially available acid type antiwear additive (containing ready denier oil acid 80-90%)
According to data in table, and cost consideration is combined, spontaneous combustion retardant most preferably composition is antioxidant 1076/nano-graphite
Powder/Span-80/ mixes durene.
Embodiment 2
Sample preparation and evaluation method be the same as Example 1.
Influence of the different component content of table 2 to spontaneous combustion resistanceization effect
Note：1) dosage 1% is added；2) experiment antiwear additive is certain commercially available acid type antiwear additive (80- containing ready denier oil acid
90%)
According to data in table, and cost consideration is combined, spontaneous combustion retardant optimal component mass ratio is antioxidant 1076:Nanometer
Graphite powder:Span‐80:Mixed durene=35:5:1:59.
Embodiment 3
Sample preparation and evaluation method be the same as Example 1.
The different test objects of table 3 and the influence to spontaneous combustion resistanceization effect for adding dosage
Note：Retardant component and content are
From table in terms of data, spontaneous combustion retardant of the present invention is effective to acid type and ester type antiwear additive.Consider, most preferably
Addition is 1-2%.Empirical tests, will be added in diesel oil added with the antiwear additive of spontaneous combustion retardant of the present invention, to diesel oil wear resistence, ten
The product physical and chemical indexs such as six alkane values, existent gum are without any adverse effect.
Claims (7)
1. a kind of prevent the compound additive of diesel antiwear additive spontaneous combustion, it is characterised in that is formed using following component compounding, respectively
Constituent mass percentage composition is：
Antioxidant 30~40%
Thermal conducting agent 5~10%
Dispersant 0~2%
Diluent 50~65%
Described antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyls）Double [3- (the 3,5- bis- of propionic acid isooctanol ester, hexylene glycol
Tert-butyl-hydroxy phenyl) propionic ester], octadecyl 3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic ester, two contracting three second two
One or more of mixtures of alcohol double [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester]；
Described thermal conducting agent is Nano graphite powder, graphene, one or more of mixtures of CNT.
2. according to the compound additive described in claim 1, it is characterised in that described dispersant be unrighted acid,
Span-80, pitch dispersant one or more of mixtures.
3. according to the compound additive described in claim 2, it is characterised in that described unrighted acid is oleic acid or sub- oil
Acid.
4. according to the compound additive described in claim 2, it is characterised in that described pitch dispersant is epoxy resin or terpene
Olefine resin.
5. according to the compound additive described in claim 1, it is characterised in that described diluent is heavy aromatics.
6. a kind of as described in claim 1-5 prevents the application process of the compound additive of diesel antiwear additive spontaneous combustion, its feature
It is, the described compound additive addition in Low sulfur diesel antiwear additive is 0.5~5%.
7. a kind of application process of compound additive for preventing diesel antiwear additive spontaneous combustion as claimed in claim 6, its feature exists
In the described compound additive addition in Low sulfur diesel antiwear additive is 1~2%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510734002.8A CN105255528B (en) | 2015-11-02 | 2015-11-02 | It is a kind of to prevent the compound additive of diesel antiwear additive spontaneous combustion |
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| CN201510734002.8A CN105255528B (en) | 2015-11-02 | 2015-11-02 | It is a kind of to prevent the compound additive of diesel antiwear additive spontaneous combustion |
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| CN105255528A CN105255528A (en) | 2016-01-20 |
| CN105255528B true CN105255528B (en) | 2017-07-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107828452A (en) * | 2017-10-27 | 2018-03-23 | 苏阳 | Environmental protection promotees the diesel fuel additives of combustion |
| CN107653012A (en) * | 2017-10-27 | 2018-02-02 | 苏阳 | Energy-saving, environment-friendly and high-efficiency promotees combustion diesel fuel additives |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1780900A (en) * | 2003-04-04 | 2006-05-31 | 罗狄亚电子与催化公司 | Colloidal dispersion of a rare earth compound comprising an anti-oxidant agent and use thereof as additive for diesel fuel for internal combustion engines |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1780900A (en) * | 2003-04-04 | 2006-05-31 | 罗狄亚电子与催化公司 | Colloidal dispersion of a rare earth compound comprising an anti-oxidant agent and use thereof as additive for diesel fuel for internal combustion engines |
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