CN106916605B - A method of PAO12 base oil is synthesized by photoinitiator TPO - Google Patents
A method of PAO12 base oil is synthesized by photoinitiator TPO Download PDFInfo
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- CN106916605B CN106916605B CN201710244542.7A CN201710244542A CN106916605B CN 106916605 B CN106916605 B CN 106916605B CN 201710244542 A CN201710244542 A CN 201710244542A CN 106916605 B CN106916605 B CN 106916605B
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- base oil
- decene
- photoinitiator
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- alkyl
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
- C10G2300/1092—C2-C4 olefins
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a kind of methods for synthesizing PAO base oil by photoinitiator TPO, it is characterised in that: puts into polymeric kettle 1- decene monomer, photoinitiator and amide, under illumination condition, polymerization reaction 8-12 hours, generates poly decene crude product；The poly decene crude product is post-treated and catalytic hydrogenation obtains viscosity PAO11 or PAO12 base oil in target.The present invention prepares PAO base oil and belongs to synthesis under normal pressure, simple process, safety coefficient height；Improve the safety of production, the present invention by photoinitiator TPO be accompanied by illumination in the way of, it is low in cost, and energy conservation and environmental protection.
Description
Technical field
The present invention relates to chemicals to synthesize field, and in particular, to a kind of preparation method of base oil, more specifically, relating to
A kind of and method that PAO12 base oil is synthesized by photoinitiator TPO.
Technical background
The base oil extracted from crude oil includes a large amount of chemical substance.Major part in these mixtures is aromatization
Object and paraffin hydrocarbon carbon compound the ingredient of thermal shocking (lubricating oil medium viscosity with) structure is closed, these substances reduce base oil
Property, and polycyclic aromatic hydrocarbon therein is carcinogen, and to environment nocuousness.
And fully synthetic PAO base oil has outstanding oxidation stability, because they are complete isomery paraffin, and does not have
There are aromatic compounds and paraffin hydrocarbon carbon compound (naphthenics) structure.Since PAO is with excellent
Elegant oxidisability and thermal stability, it is widely used in the field of fine industrial goods manufacture.
In industrial aspect, PAO extends the drain period according to the service life of lube container, therefore, reduces shut-down
Loss, in addition, PAO is still able to maintain good mobility in very low temperatures, so PAO engine lubricating oil is with good
Cold starting performance.Use lubricating oil oily based on PAO, engine energy quick start, lubricating oil can moment in place etc.
A little.
Currently, PAO base oil is fully synthetic, and often using metallocene as catalyst, although reaction speed ratio is very fast,
Be it is at high cost, be unfavorable for industrialized production；Such as use BF3、TiCl4When equal catalyst synthesis PAO base oil, although can reach
The requirement of low viscosity, but use the catalyst danger coefficient high；In addition, existing preparation PAO base oil method is typically necessary
Compressive reaction, safety coefficient is low, and more demanding to the technique of operative employee, be easy to cause production safety problem.
Summary of the invention
The present invention aims to overcome the above drawbacks, using the modified alchlor of Loprazolam as catalyst, can efficiently close
At PAO base oil, the constraint of traditional reaction time length is got rid of.
The present invention provides a kind of methods for synthesizing PAO base oil by photoinitiator TPO, it is characterised in that: by 1- decene
In monomer, photoinitiator and amide investment polymeric kettle, under illumination condition, polymerization reaction 8-12 hours, generates poly decene and slightly produce
Product；
Above-mentioned poly decene crude product is post-treated and catalytic hydrogenation obtains the basis viscosity PAO11 or PAO12 in target
Oil.
Further, a kind of method synthesizing PAO base oil by photoinitiator TPO provided by the invention also has in this way
The characteristics of: i.e., the molar ratio of above-mentioned photoinitiator and amide be 1:0.05-0.1.
Preferred photoinitiator and the molar ratio of amide are 1:0.06-0.09.
Further, a kind of method synthesizing PAO base oil by photoinitiator TPO provided by the invention also has in this way
The characteristics of: i.e., the mass ratio of above-mentioned 1- decene monomer and photoinitiator be 97-100:0.8-2.
It is preferred that the mass ratio of 1- decene monomer and photoinitiator is 98:1-1.5.
Further, a kind of method synthesizing PAO base oil by photoinitiator TPO provided by the invention also has in this way
The characteristics of: i.e., above-mentioned amide be such as flowering structure compound represented:
Wherein, R1 is selected from hydrogen, alkyl；
R2 is selected from hydrogen, alkyl；
R3 is selected from hydrogen, alkyl.
Further, a kind of method synthesizing PAO base oil by photoinitiator TPO provided by the invention also has in this way
The characteristics of: i.e., above-mentioned R1 be selected from carbon atom number be not more than 4 alkyl；
The alkyl or unsaturated alkyl that R2 is selected from hydrogen, carbon atom number is 1-18；
The alkyl or unsaturated alkyl that R3 is selected from hydrogen, carbon atom number is 1-18.
Further, a kind of method synthesizing PAO base oil by photoinitiator TPO provided by the invention also has in this way
The characteristics of: i.e., above-mentioned poly decene crude product post-processing process are as follows: by poly decene crude product through filtering remove solid impurity, lead to
Cross the isolated vacuum distillation product of mode and unreacted 1- decene monomer of vacuum distillation；
Wherein, unreacted 1- decene monomer can be recycled.
Further, a kind of method synthesizing PAO base oil by photoinitiator TPO provided by the invention also has in this way
The characteristics of: i.e., the process of above-mentioned catalytic hydrogenation are as follows: vacuum distillation product mix pressurization with hydrogen, is directly entered to be equipped with and is added hydrogen
The device of catalyst, 120-150 DEG C of feeding temperature, hydrogen partial pressure 6-11MPa, volume space velocity about 0.5-1h-1, hydrogen to oil volume ratio
400-300:1, hydrogenated catalysis removal of impurities obtain target PAO base oil.
Further, a kind of method synthesizing PAO base oil by photoinitiator TPO provided by the invention also has in this way
The characteristics of: i.e., above-mentioned 1- decene monomer may alternatively be any alpha-olefin.When different 1- decene monomers is as polymerized monomer
When, different middle viscosity base oils can be obtained under different reaction conditions.
The function and effect of the present invention:
The present invention prepares PAO base oil, simple process, safety coefficient height；The safety of production is improved, the present invention utilizes
Photoinitiator TPO is accompanied by the mode of illumination, low in cost, and energy conservation and environmental protection.
In addition, reaction condition of the present invention is mild, reaction is can be completed in synthesis under normal pressure, and the product viscosity of acquisition is easily controllable,
The viscosity of product can controlled into the level in midium-viscosity by the reactive mode, and post-processing is convenient.
In addition, in the present invention, also having selected the catalysis scheme of amide cooperation photoinitiator, in this scenario, amide groups
By photocatalysis, the effect for promoting the further polymerization reaction of active group in alkene can be played.
In addition, the problem not high compared to viscosity oil product yield in conventional synthesis, oil product manufactured by method of the invention,
Yield is generally greater than 80%.
Specific embodiment
Embodiment 1
5000g 1- decene monomer, 80g photoinitiator TPO and 10g acrylamide are put into reaction kettle, illumination condition 12
After a hour, polymerization reaction generates poly decene crude product.
Poly decene crude product removes part photoinitiator through filtering, and residue enters rotary evaporator and is evaporated under reduced pressure, gas
The isolated PAO base oil of liquid and unreacted 1- decene compound monomer, unreacted 1- decene compound monomer again into
Enter polymeric kettle and polymerization reaction occurs.
Vacuum distillation product is pressurized to be directly entered the device equipped with hydrogenation catalyst, feeding temperature 140 in hydrogen mixing
DEG C, hydrogen partial pressure 8MPa, volume space velocity about 0.5h-1, hydrogen to oil volume ratio 400:1, hydrogenated catalysis removal of impurities preparation PAO11 is main base
Plinth oil (yield 89%).
Embodiment 2
5200g 1- decene monomer, 100g photoinitiator TPO and 25g acrylamide are put into reaction kettle, illumination condition 8
After a hour, polymerization reaction generates poly decene crude product.
Poly decene crude product removes part photoinitiator through filtering, and residue enters rotary evaporator and is evaporated under reduced pressure, gas
The isolated PAO base oil of liquid and unreacted 1- decene compound monomer, unreacted 1- decene compound monomer again into
Enter polymeric kettle and polymerization reaction occurs.
Vacuum distillation product is pressurized to be directly entered the device equipped with hydrogenation catalyst, feeding temperature 140 in hydrogen mixing
DEG C, hydrogen partial pressure 8MPa, volume space velocity about 0.5h-1, hydrogen to oil volume ratio 400:1, hydrogenated catalysis removal of impurities preparation PAO12 is main base
Plinth oil (yield 82%).
Embodiment 3
4900g 1- decene monomer, 110g photoinitiator TPO and 15g Methacrylamide are put into reaction kettle, illumination
After 10 hours of condition, polymerization reaction generates poly decene crude product.
Poly decene crude product removes part photoinitiator through filtering, and residue enters rotary evaporator and is evaporated under reduced pressure, gas
The isolated PAO base oil of liquid and unreacted 1- decene compound monomer, unreacted 1- decene compound monomer again into
Enter polymeric kettle and polymerization reaction occurs.
Vacuum distillation product is pressurized to be directly entered the device equipped with hydrogenation catalyst, feeding temperature 140 in hydrogen mixing
DEG C, hydrogen partial pressure 8MPa, volume space velocity about 0.5h-1, hydrogen to oil volume ratio 400:1, hydrogenated catalysis removal of impurities preparation PAO12 is main base
Plinth oil (yield 81%).
Embodiment 4
4900g 1- decene monomer, 110g photoinitiator TPO and 55g dodecylacrylamide are put into reaction kettle,
After 12 hours of illumination condition, polymerization reaction generates poly decene crude product.
Poly decene crude product removes part photoinitiator through filtering, and residue enters rotary evaporator and is evaporated under reduced pressure, gas
The isolated PAO base oil of liquid and unreacted 1- decene compound monomer, unreacted 1- decene compound monomer again into
Enter polymeric kettle and polymerization reaction occurs.
Vacuum distillation product is pressurized to be directly entered the device equipped with hydrogenation catalyst, feeding temperature 150 in hydrogen mixing
DEG C, hydrogen partial pressure 15MPa, volume space velocity about 0.5h-1, hydrogen to oil volume ratio 300:1, based on hydrogenated catalysis removal of impurities preparation PAO12
Base oil (yield 75%).
Claims (6)
1. a kind of method for synthesizing PAO base oil by photoinitiator TPO, it is characterised in that:
1- decene monomer, photoinitiator and amide are put into polymeric kettle, it is polymerization reaction 8-12 hours, raw under illumination condition
At poly decene crude product；
The poly decene crude product is post-treated and catalytic hydrogenation obtains viscosity PAO11 or PAO12 base oil in target；
The molar ratio of the photoinitiator and amide is 1:0.05-0.1；
The mass ratio of the 1- decene monomer and photoinitiator is 97-100:0.8-2.
2. a kind of method for synthesizing PAO base oil by photoinitiator TPO as described in claim 1, it is characterised in that:
The amide is such as flowering structure compound represented:
Wherein, R1Selected from hydrogen, alkyl；
R2Selected from hydrogen, alkyl；
R3Selected from hydrogen, alkyl.
3. a kind of method for synthesizing PAO base oil by photoinitiator TPO as claimed in claim 2, it is characterised in that:
The R1It is not more than 4 alkyl selected from carbon atom number；
R2Selected from hydrogen, the alkyl or unsaturated alkyl that carbon atom number is 1-18；
R3Selected from hydrogen, the alkyl or unsaturated alkyl that carbon atom number is 1-18.
4. a kind of method for synthesizing PAO base oil by photoinitiator TPO as described in claim 1, it is characterised in that:
The process of the poly decene crude product post-processing are as follows: poly decene crude product is removed into solid impurity through filtering, passes through decompression
The isolated vacuum distillation product of the mode of distillation and unreacted 1- decene monomer；
Wherein, unreacted 1- decene monomer is recycled.
5. a kind of method for synthesizing PAO base oil by photoinitiator TPO as claimed in claim 4, it is characterised in that:
The process of the catalytic hydrogenation are as follows: vacuum distillation product is mixed pressurization with hydrogen, is directly entered equipped with hydrogenation catalyst
Device, 120-150 DEG C of feeding temperature, hydrogen partial pressure 6-11MPa, volume space velocity 0.5-1h-1, hydrogen to oil volume ratio 400-300:1,
Hydrogenated catalysis removal of impurities obtains target PAO base oil.
6. a kind of method for synthesizing PAO base oil by photoinitiator TPO a method as claimed in any one of claims 1 to 5, it is characterised in that:
The 1- decene monomer is replaced by any alpha-olefin.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710244542.7A CN106916605B (en) | 2017-04-14 | 2017-04-14 | A method of PAO12 base oil is synthesized by photoinitiator TPO |
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| CN201710244542.7A CN106916605B (en) | 2017-04-14 | 2017-04-14 | A method of PAO12 base oil is synthesized by photoinitiator TPO |
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| CN106916605B true CN106916605B (en) | 2019-01-18 |
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| US5171908A (en) * | 1991-11-18 | 1992-12-15 | Mobil Oil Corporation | Synthetic polyolefin lubricant oil |
| CN1425056A (en) * | 1999-12-22 | 2003-06-18 | 切夫里昂美国公司 | Process for making lube base stock from lower molecular weight feedstock |
| CN101932623A (en) * | 2008-01-17 | 2010-12-29 | 巴斯夫欧洲公司 | Modified olefin polymers |
| CN103298840A (en) * | 2010-10-19 | 2013-09-11 | 马克斯·普朗克科学促进学会 | Process for the modification of polymers, in particular polymer nanoparticles |
| CN104250564A (en) * | 2013-06-26 | 2014-12-31 | 中国石油化工股份有限公司 | Method for synthesis of poly alpha-olefin lubricating oil base oil |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7456329B2 (en) * | 2005-11-30 | 2008-11-25 | Exxonmobil Chemical Patents Inc. | Polyolefins from non-conventional feeds |
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2017
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| US5171908A (en) * | 1991-11-18 | 1992-12-15 | Mobil Oil Corporation | Synthetic polyolefin lubricant oil |
| CN1425056A (en) * | 1999-12-22 | 2003-06-18 | 切夫里昂美国公司 | Process for making lube base stock from lower molecular weight feedstock |
| CN101932623A (en) * | 2008-01-17 | 2010-12-29 | 巴斯夫欧洲公司 | Modified olefin polymers |
| CN103298840A (en) * | 2010-10-19 | 2013-09-11 | 马克斯·普朗克科学促进学会 | Process for the modification of polymers, in particular polymer nanoparticles |
| CN104250564A (en) * | 2013-06-26 | 2014-12-31 | 中国石油化工股份有限公司 | Method for synthesis of poly alpha-olefin lubricating oil base oil |
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