CN105219432B - A kind of method improving bio oil lubricity - Google Patents
A kind of method improving bio oil lubricity Download PDFInfo
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- CN105219432B CN105219432B CN201510582226.1A CN201510582226A CN105219432B CN 105219432 B CN105219432 B CN 105219432B CN 201510582226 A CN201510582226 A CN 201510582226A CN 105219432 B CN105219432 B CN 105219432B
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Abstract
The invention discloses a kind of method improving bio oil lubricity, including modification, refined, 3 unit operations of dispersion, first catalyst, modifying agent are added prepared modification biological oil in pressure reaction still, then modification biological oil is carried out decompression distillation reaction and obtains refining biological oil, refining biological oil will add lubrication reinforcing agent, dispersant again, after ultrasonic disperse is uniform, high shear agitation.The method of the present invention is easy and simple to handle, it is easy to large-scale production, can significantly improve bio oil lubricity, and the bio oil after upgrading can form continuous oil film, friction pair coefficient of friction and wear extent at frictional interface and reduce by more than 40%, has a good application prospect.
Description
One, technical field
The present invention relates to biomass energy source domain, a kind of method improving bio oil lubricity.
Two, background technology
Bio oil is a kind of new liquid energy that various living beings are prepared through methods such as pyrolysis liquefactions, have renewable,
It is zero clear superiority such as grade that carbon discharges only.But due to bio oil complicated component, one of them is it is a key issue that bio oil exists
Metal surface filming performance is poor, and lubricity is not enough, had a strong impact on some typical mechanical part such as engine nozzles,
Rotary pump, dispensing pump etc. properly functioning, causes its application in automobile engine to be restricted, therefore, and bio oil
Lubricity in the urgent need to being improved, to accelerate the application on automobile of this novel energy.
At present, the method improving bio oil lubricity mainly uses and fossil energy blending, and even now can be to a certain degree
The lubricity of upper increase bio oil, but the utilization rate of bio oil is restricted, and fossil energy to be relied on；China
Patent (CN104212501) discloses a kind of diesel fuel lubricity modifier, it is possible to be effectively improved diesel fuel lubricity so that
Wear scar diameter under high-frequency reciprocating experimental condition is less than 460 μm, uses aphthenic acids and naphthenic acid esters by percent mass
Mix than the ratio of 10～30%: 90～70%, the modifier obtained after adding thermal agitation 1～2h at 50～80 DEG C,
Diesel fuel lubricity can be improved.Chinese patent (CN104371776) also discloses that a kind of Lubricity of Low-Sulfur Diesel Fuels that improves
Method, adds the amino polyacid of 10mg/kg～2000mg/kg and the condensation reaction products of amine in low-sulfur diesel-oil, with
Use grease to compare as antiwear additive and can be obviously improved diesel fuel lubricity.But, owing to bio oil and diesel fuel composition differ relatively
Greatly, these methods improving diesel fuel lubricity are difficult to prove effective in bio oil.Although by adding some lubricant at biology
Oil also can improve the lubricity of bio oil, but due to the complicated component of bio oil, these additives are in bio oil
Dispersiveness, compatibility, stability problem are not well solved, therefore, it is necessary to it is raw to develop a kind of new raising
The method of thing oil lubricity.
Three, summary of the invention
The present invention is directed to the present situation that bio oil lubricity is not enough, purpose seeks to provide a kind of side improving bio oil lubricity
Method, to promote the application of bio oil.
The present invention is achieved through the following technical solutions:
A kind of method improving bio oil lubricity, including modification, refined, 3 unit operations of dispersion, concrete, change
Property is on the basis of bio oil, 50～200mg/kg catalyst, 2～100g/kg modifying agent is sequentially added in bio oil,
After stirring, being placed in pressure reaction still, at 120～150 DEG C, stirring reaction 30～60min, is warming up to 300～400 DEG C
Lower stirring reaction 20～30min, cooled and filtered, centrifugal segregation catalyst and aqueous phase, obtain modification biological oil；Refined
It is that modification biological oil is moved to decompression distillation system, at 50～60 DEG C of distillation reactions 12～24h that reduce pressure, collects in receiving bottle
Obtain refining biological oil；Dispersion is to be separately added into 20～500mg/kg lubrication reinforcing agents, 1～80mg/kg in refining biological oil
Dispersant, after ultrasonic disperse 10～20min, high shear agitation 20～30min.
Described bio oil is that Wooden Biomass is prepared by rapidly pyrolysing and liquefying, its chemical composition contain acid,
Alcohol, aldehyde, ketone, hydrocarbon, phenol, ester, pH value is less than 5, and oxygen content is more than 15%；Described catalyst is KF-Ni/ZSM-5,
Its preparation method is containing 1mol/L KF and 0.5mol/L NiSO at 1L4Solution in put into 100g ZSM-5, stirring is all
After even, regulation pH value of solution is 10, and 12h is soaked in absorption, filters, by gained solid at H2Atmosphere, 700～800 DEG C
Tube furnace is calcined 2h；Described modifying agent be carbon number be C6～the C12 hydroxyl straight dihydric alcohol at two ends.
The pressure of described decompression distillation reaction is 0.5～1.0kPa；Described high shear agitation speed is
20000～22000rpm.
Described lubrication reinforcing agent is the Fe of particle diameter 80～800nm3O4@MoS2Nanosphere and particle diameter 1～10 μm MoS2Micro-
The mixture of rice sheet, their mass ratio is 1: 0.2～5, wherein Fe3O4@MoS2The preparation method of nanosphere is will
The Fe of 11.55g particle diameter 10nm3O4Join 1L containing 0.1mol/L sodium molybdate, the hydro-thermal reaction of 0.2mol/L vulcanized sodium
In still, in 260 DEG C of stirring reaction 2h, centrifugal, water washing and precipitating thing, drying.
Described dispersant is glycerin monostearate and the mixture that Tween 80 mass ratio is 1: 0.5～2.
Compared with prior art, the invention has the beneficial effects as follows:
1) bio oil lubricity is promoted effective by the method for the present invention.Bio oil after upgrading can be formed at frictional interface
Continuous oil film, average oil film percentage reaches more than 75%, friction pair coefficient of friction with wear extent relative to the bio oil before upgrading
More than 40% can be reduced.
2) additive that the method for the present invention is used is long in bio oil good dispersion, stabilization time.Lubrication reinforcing agent exists
Without obvious agglomeration in bio oil, add in bio oil and can stablize more than 1 month.
3) method of the present invention is simple to operate, it is easy to large-scale promotion.The method of the present invention is by modified, refined, dispersion
Deng three basic chemical engineering unit operations, the existing equipment of common oil product manufacturing enterprise all can meet, it is not necessary to newly-increased investment.
Four, specific embodiment
For a better understanding of the present invention, by specific examples below, the present invention is described, is not limiting as the present invention；Following institute
Bio oil come from prepared by rice husk rapidly pyrolysing and liquefying method, its composition through compounds GC-MS detect peak area phase
To percentage it is: acids 20.5%, alcohols 3.6%, aldehydes 21.3%, ketone 31.5%, hydro carbons 2.6%, phenols 20.2%,
Esters 0.3%, pH4.5, oxygen content 21.2%；The preparation method of KF-Ni/ZSM-5 be 1L containing 1mol/L KF and
0.5mol/L NiSO4Solution in put into 100g ZSM-5, after stirring, regulation pH value of solution be 10, absorption soak
12h, filters, by gained solid at H2Atmosphere, the tube furnace of 700～800 DEG C are calcined 2h and get final product；Fe3O4@MoS2
The preparation method of nanosphere is by the Fe of 11.55g particle diameter 10nm3O4Join 1L containing 0.1mol/L sodium molybdate, 0.2
In the hydrothermal reaction kettle of mol/L vulcanized sodium, in 260 DEG C of stirring reaction 2h, centrifugal, water washing and precipitating thing, drying.
Embodiment 1:
By 50mg KF-Ni/ZSM-5,10g 1,6-hexylene glycol is sequentially added in 1kg bio oil, after stirring, is placed in
In pressure reaction still, stirring reaction 45min at 120 DEG C, it is warming up at 320 DEG C stirring reaction 30min, after cooling
Filtration, centrifugal segregation catalyst and aqueous phase, obtain modification biological oil；Modification biological oil is moved to decompression distillation system,
50 DEG C, 0.8kPa reduces pressure distillation reaction 12h, collects in receiving bottle and obtains refining biological oil；In refining biological oil respectively
Add the particle diameter 80～800nmFe that 50mg mass ratio is 1: 0.23O4@MoS2Nanosphere and particle diameter 1～10 μm MoS2
The mixture of micron film, 10mg mass ratio are the mixture of 1: 0.5 glycerin monostearate and Tween 80, ultrasonic point
After dissipating 10min, 20000rpm high shear agitation 20min.
Embodiment 2:
By 100mg KF-Ni/ZSM-5,20g 1,8-ethohexadiol is sequentially added in 1kg bio oil, after stirring, puts
In pressure reaction still, stirring reaction 40min at 130 DEG C, it is warming up at 350 DEG C stirring reaction 20min, cooling
Rear filtration, centrifugal segregation catalyst and aqueous phase, obtain modification biological oil；Modification biological oil is moved to decompression distillation system,
At 50 DEG C, 0.6kPa reduces pressure distillation reaction 12h, collects in receiving bottle and obtains refining biological oil；Divide in refining biological oil
Not Jia Ru 80mg mass ratio be 1: 1 the Fe of particle diameter 80～800nm3O4@MoS2Nanosphere and particle diameter
1～10 μm MoS2The mixture of micron film, 20mg mass ratio are the mixing of 1: 2 glycerin monostearate and Tween 80
Thing, after ultrasonic disperse 15min, 22000rpm high shear agitation 30min.
Embodiment 3:
By 200mg KF-Ni/ZSM-5,100g 1,9-nonanediol is sequentially added in 1kg bio oil, after stirring, puts
In pressure reaction still, stirring reaction 60min at 150 DEG C, it is warming up at 380 DEG C stirring reaction 30min, cooling
Rear filtration, centrifugal segregation catalyst and aqueous phase, obtain modification biological oil；Modification biological oil is moved to decompression distillation system,
At 60 DEG C, 1kPa reduces pressure distillation reaction 20h, collects in receiving bottle and obtains refining biological oil；Divide in refining biological oil
Not Jia Ru 200mg mass ratio be 1: 1 the Fe of particle diameter 80～800nm3O4@MoS2Nanosphere and particle diameter
1～10 μm MoS2The mixture of micron film, 70mg mass ratio are the mixing of 1: 1 glycerin monostearate and Tween 80
Thing, after ultrasonic disperse 20min, 22000rpm high shear agitation 20min.
Performance before and after bio oil upgrading is as shown in table 1, there it can be seen that biological after the upgrading that obtains of the inventive method
In oil, additive dispersion effect is good, oil product good stability；Compared with before upgrading, the bio oil after upgrading can be at frictional interface
Forming more complete oil film, coefficient of friction and the wear extent of friction pair decrease beyond 40%, show that the inventive method can be notable
Improve the lubricity of bio oil.
Table 1: bio oil performance
Claims (5)
1. the method improving bio oil lubricity, it is characterised in that on the basis of bio oil, will
50～200mg/kg catalyst, 2～100g/kg modifying agent are sequentially added in bio oil, after stirring, are placed in
In pressure reaction still, at 120～150 DEG C, stirring reaction 30～60min, is warming up at 300～400 DEG C stirring
Reaction 20～30min, cooled and filtered, centrifugal segregation catalyst and aqueous phase obtain modification biological oil, by modification
Bio oil moves to decompression distillation system, at 50～60 DEG C of distillation reactions 12～24h that reduce pressure, collects in receiving bottle and obtains
The refining biological oil arrived, then toward refining biological oil is separately added into 20～500mg/kg lubrication reinforcing agents,
1～80mg/kg dispersant, after ultrasonic disperse 10～20min, high shear agitation 20～30min；Wherein
Described catalyst is KF-Ni/ZSM-5, and its preparation method is at 1L KF and 0.5mol/L Han 1mol/L
NiSO4Solution in put into 100g ZSM-5, after stirring, regulation pH value of solution be 10, absorption soak
12h, filters, by gained solid at H2Atmosphere, the tube furnace of 700～800 DEG C are calcined 2h；Described modification
Agent be carbon number be C6～the C12 hydroxyl straight dihydric alcohol at two ends.
The method of raising bio oil lubricity the most according to claim 1, it is characterised in that described
Bio oil is that Wooden Biomass is prepared by rapidly pyrolysing and liquefying, its chemical composition contain acid, alcohol,
Aldehyde, ketone, hydrocarbon, phenol, ester, pH value is less than 5, and oxygen content is more than 15%.
The method of raising bio oil lubricity the most according to claim 1, it is characterised in that described
The pressure of decompression distillation reaction is 0.5～1.0kPa；Described high shear agitation speed is
20000～22000rpm.
The method of raising bio oil lubricity the most according to claim 1, it is characterised in that described
Lubrication reinforcing agent is the Fe of particle diameter 80～800nm3O4@MoS2Nanosphere and particle diameter 1～10 μm MoS2Micron
The mixture of sheet, their mass ratio is 1: 0.2～5, wherein Fe3O4@MoS2The preparation method of nanosphere is
Fe by 11.55g particle diameter 10nm3O4Join 1L containing 0.1mol/L sodium molybdate, 0.2mol/L vulcanized sodium
In hydrothermal reaction kettle, in 260 DEG C of stirring reaction 2h, centrifugal, water washing and precipitating thing, drying.
The method of raising bio oil lubricity the most according to claim 1, it is characterised in that described
Dispersant is glycerin monostearate and the mixture that Tween 80 mass ratio is 1: 0.5～2.
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| CN101338224A (en) * | 2007-07-03 | 2009-01-07 | 上海申旭特种机用燃料有限公司 | Bio liquid fuel |
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| CN102021073A (en) * | 2010-09-15 | 2011-04-20 | 合肥工业大学 | Preparation method of dispersing nano molybdenum disulfide in lubricating oil system |
| CN103343055A (en) * | 2013-06-24 | 2013-10-09 | 合肥工业大学 | Method for quality improvement of biological oil through catalytic esterification-deoxidize reforming in subcritical alcohol system |
| CN103459562A (en) * | 2010-11-04 | 2013-12-18 | 雅宝欧洲有限责任公司 | Hydrodeoxygenation of pyrolysis oil in presence of admixed alcohol |
| WO2015028682A1 (en) * | 2013-09-02 | 2015-03-05 | Shell Internationale Research Maatschappij B.V. | Process for preparing a catalyst, catalyst obtained by such process, and use of such catalyst |
| CN104450069A (en) * | 2014-11-14 | 2015-03-25 | 合肥工业大学 | Environment-friendly lubricating oil taking bio-oil as base oil and preparation method of lubricating oil |
-
2015
- 2015-09-11 CN CN201510582226.1A patent/CN105219432B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338224A (en) * | 2007-07-03 | 2009-01-07 | 上海申旭特种机用燃料有限公司 | Bio liquid fuel |
| CN101899334A (en) * | 2010-07-14 | 2010-12-01 | 青岛大学 | Biomass pyrolysis oil refining method |
| CN102021073A (en) * | 2010-09-15 | 2011-04-20 | 合肥工业大学 | Preparation method of dispersing nano molybdenum disulfide in lubricating oil system |
| CN103459562A (en) * | 2010-11-04 | 2013-12-18 | 雅宝欧洲有限责任公司 | Hydrodeoxygenation of pyrolysis oil in presence of admixed alcohol |
| CN103343055A (en) * | 2013-06-24 | 2013-10-09 | 合肥工业大学 | Method for quality improvement of biological oil through catalytic esterification-deoxidize reforming in subcritical alcohol system |
| WO2015028682A1 (en) * | 2013-09-02 | 2015-03-05 | Shell Internationale Research Maatschappij B.V. | Process for preparing a catalyst, catalyst obtained by such process, and use of such catalyst |
| CN104450069A (en) * | 2014-11-14 | 2015-03-25 | 合肥工业大学 | Environment-friendly lubricating oil taking bio-oil as base oil and preparation method of lubricating oil |
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