CN101054332B - Method of synthesizing poly alpha-olefin oil - Google Patents

Method of synthesizing poly alpha-olefin oil Download PDF

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Publication number
CN101054332B
CN101054332B CN2006100728743A CN200610072874A CN101054332B CN 101054332 B CN101054332 B CN 101054332B CN 2006100728743 A CN2006100728743 A CN 2006100728743A CN 200610072874 A CN200610072874 A CN 200610072874A CN 101054332 B CN101054332 B CN 101054332B
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oil
olefin
reactor
reaction
initiator
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CN101054332A (en
Inventor
曾世虎
李绍凡
张志峰
丁洪生
刘伟
谢云发
陈新德
权成光
李成俭
高桂芝
许兰香
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CNPC Fushun Petrochemical Co
Liaoning Shihua University
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CNPC Fushun Petrochemical Co
Liaoning Shihua University
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Abstract

The invention relates to a method for synthesizing poly-Alpha-olefin oil taking BF3 promoters as catalysts and olefins as raw materials, which is characterized by that weight rate of alcohol dosage used for initiating agent to olefin hydrocarbon is 0.01 to 1.0%; the weight rate of BF3 dosage to the raw materials of olefin hydrocarbon is1 to 5%; a reaction temperature is 0 to 80 DEG C; a reaction pressure is 0 to 1.0MPa; a reaction time is 1 to 6h, a technological line of two kettle parallel connection and evaporation-adsorption series connection is adopted, a polymerized oil is added an absorption kettle, 2-5% of white clay is added, the mixture is fully stirred under the temperature of 60 DEG C, and after 30 min, the materials are fed to a product tank through a filter. The present method optimizes a catalyst system, technological conditions and process flow of BF3 catalyzed synthesizing poly-Alpha-olefin oil, wherein the oil product has the advantages of low viscosity, low-freezing, high viscosity index, good oxidation stability, light color and high yield, and the BF3 catalyst is capable of recycling use and accords with environmental requirements.

Description

A kind of method of synthesizing poly alpha-olefin oil
Technical field
The present invention relates to a kind of with boron trifluoride (BF 3) promotor is catalyzer, alkene is the method for raw material synthesizing poly alpha-olefin oil (PAO).
Background technology
Poly ﹠ Alpha ,-olefin oil (PAO) is compared with mineral oil, has good physics, chemical property, therefore is used widely.And, also having promoted developing rapidly of poly ﹠ Alpha ,-olefin oil (PAO) in recent years along with energy-conservation and environmental requirement increasingly stringent, annual speed with 10～15% increases rapidly.
The preparation of poly ﹠ Alpha ,-olefin oil (PAO) is carried out in two steps, and the first step is alkene oligomerisation under the effect of catalyzer, obtains the unsaturated hydrocarbons of oligomerisation; Second step was with the double-bond hydrogenation in the unsaturated hydrocarbons of oligomerisation, thereby improved the thermo-oxidative stability of poly ﹠ Alpha ,-olefin oil (PAO).
The production of present domestic poly ﹠ Alpha ,-olefin oil is to be raw material with the waxcrack, adopts AlCl 3Catalyzer is main.Problems such as this Catalyst Production poly ﹠ Alpha ,-olefin oil exists and causes easily that equipment corrosion, environmental pollution are serious, aluminium slag many (reaching 5%) and difficult processing, and owing to be accompanied by a large amount of side reactions in the reaction process, it is complicated to cause polymkeric substance to be formed, aspects such as this point outstanding behaviours is low in the viscosity index of oil product, thermal oxidation stability does not pass a test, its performance are compared with external poly ﹠ Alpha ,-olefin oil (PAO) and are existed the certain quality gap.Therefore develop poly ﹠ Alpha ,-olefin oil (PAO) novel process and make its industrialization, can promote the product specification of China's poly ﹠ Alpha ,-olefin oil (PAO) comprehensively, for the domestic market provides high-quality poly ﹠ Alpha ,-olefin oil (PAO), reduce the production cost of high-grade I. C. engine oil, economical, societal benefits also are the demands of social development and national defense industry with highly significant
Summary of the invention
The objective of the invention is to develop with boron trifluoride (BF 3) promotor is catalyzer, alkene is raw material synthesizing poly alpha-olefin oil (PAO) technology, makes the oil viscosity index reached more than 120.
Determine with alcohol to be initiator, with BF 3Alcohol complex is a catalyzer, is raw material synthesizing poly alpha-olefin oil (PAO) with alkene.Alcohol is methyl alcohol, ethanol, propyl alcohol, butanols or amylalcohol.
Processing condition are as follows.
The weight ratio of initiator amount and raw material olefin is 0.01～1.0%
BF 3The weight ratio of consumption and raw material olefin is 1-5%
0～80 ℃ of temperature of reaction
Reaction pressure 0～1.0Mpa
Reaction times 1～6h
Novel process adopts two still parallel connections, evaporation-absorption series connection to be the operational path of characteristics, and catalyzer can be recycled, and no washing, alkali cleaning, oil water separation process and wastewater treatment process are pollution-free, environmentally friendly.
Raw material olefin is head tank in the Vehicle loaded pump feeder, and the head tank internal olefin is sent into reactor through feedstock pump, and initiator is pumped into reactor from the initiator jar through initiator simultaneously, fully stirs.Charge into BF 3Gas continues to stir, and keeps certain reaction pressure, and by circulating water cooling system, control certain reaction temperature, reaction certain hour.
After reaction finishes, with BF residual in the reactor 3Gas is sent into the water-cooled jar, and by the heating to reactor, makes BF as much as possible 3Gas enters the water-cooled jar, cooled BF 3The compressed machine of gas enters second reactor (charging), fully stirs, and makes the residual BF of its absorption first reactor as much as possible 3Gas will cause a jar interior initiator then and be pumped into second reactor through initiator, fill BF 3Gas carries out the reaction second time.
Stand oil in first reactor is pumped into the absorption still at the bottom of still, add 2～5% carclazyte, under 60 ℃ of conditions, fully stirs, and after 30 minutes material is sent into the product jar through filter.Optimized BF 3Catalysis synthesizing poly alpha-olefin oil (PAO) catalyst system, processing condition and technical process, oil product have lowly sticking, low coagulates, high viscosity index (HVI), the good high advantage of oxidation stability, lighter color, yield; BF 3Catalyzer can be recycled, and whole technology is pollution-free, compliance with environmental protection requirements.
Description of drawings
Fig. 1 synthesizing poly alpha-olefin oil process flow sheet
Embodiment
Embodiment 1
By following processing condition, with C 8～13Alkene is raw material, with BF 3Propyl alcohol promotor is that catalyzer carries out synthesizing poly alpha-olefin oil (PAO) experiment.
50 ℃ of polymerization temperatures
Reaction pressure 0.0Mpa
Reaction times 1h
Propyl alcohol consumption 0.8%
BF 3Consumption 1%
60 ℃ of extraction temperatures
Refining time 0.5h
Carclazyte consumption 3% relative stand oil
The oil product material balance sees the following form.
Material balance
Project Material balance
Raw material olefin, % 100
The refining oil that overlaps, % is wherein:＞280 ℃ of fraction＜280 ℃ fractions 94 85 9
Residue, % 3
Loss (containing clay dregs), % 3
The catalyst consumption amount, % 1
Oil property sees the following form.
＞280 ℃ of fraction character
Project Oil property
Kinematic viscosity, mm 2/s 40℃ 100℃ 20.14 4.03
Viscosity index 124
Flash-point (opening), ℃ 164
Condensation point, ℃ -66
Bromine number, gBr/100g 28.74
Carbon residue, % 0.034
Colorimetric 6.0
Rotary oxygen bomb (150 ℃), min 145
Oil product is as follows by material balance and oil property behind the following processing condition hydrogenation.
The hydrogenation technique condition
Catalyzer Temperature of reaction Reaction pressure Hydrogen-oil ratio Air speed
3996 270℃ 4.0MPa 500∶1 0.5h -1
Material balance behind the hydrogenation
＜280 ℃ of fractions PAO-2 PAO-4 PAO-6 Loss
10％ 22％ 41％ 26％ 1％
Each component product property behind the hydrogenation fractionating
Project PAO-2 PAO-4 PAO-6
Each component product property behind the hydrogenation fractionating
Kinematic viscosity, mm 2/s 40℃ 100℃ 7.41 2.26 18.73 4.03 36.98 6.48
Viscosity index 118 125 127
Condensation point, ℃ -60 -68 -62
Flash-point (opening), ℃ 180 210 230
The bromine valency, gBr/100g 0.015 0.015 0.015
Colorimetric, number ＜0.5 ＜0.5 ＜0.5
Carbon residue, % 0.008 0.012 0.013
Rotary oxygen bomb (150 ℃), min 440 435 444
Embodiment 2
By following processing condition, with C 8～13Alkene is raw material, with BF 3Butanols promotor is that catalyzer carries out synthesizing poly alpha-olefin oil (PAO) experiment.
30 ℃ of polymerization temperatures
Reaction pressure 0.4Mpa
Reaction times 3h
BF 3Consumption 5%
Butanols consumption 0.1%
60 ℃ of extraction temperatures
Refining time 0.5h
Carclazyte consumption 3% (stand oil relatively)
The oil product material balance sees the following form.
Material balance
Project Material balance
Raw material olefin, % 100
The refining oil that overlaps, % is wherein:＞280 ℃ of fraction＜280 ℃ fractions 94 86 8
Residue, % 3
Loss (containing clay dregs), % 3
The catalyst consumption amount, % 1
Oil property sees the following form.
＞280 ℃ of fraction character
Project Oil property
Kinematic viscosity, mm 2/s 40℃ 100℃ 20.14 4.03
Viscosity index 124
Flash-point (opening), ℃ 172
Condensation point, ℃ -62
Bromine number, gBr/100g 28.74
Carbon residue, % 0.036
Colorimetric 6.0
Rotary oxygen bomb (150 ℃), min 147
Oil product is as follows by material balance and oil property behind the following processing condition hydrogenation.
The hydrogenation technique condition
Catalyzer Temperature of reaction Reaction pressure Hydrogen-oil ratio Air speed
3996 270℃ 4.0MPa 500∶1 0.5h -1
Material balance behind the hydrogenation
＜280 ℃ of fractions PAO-2 PAO-4 PAO-6 Loss
8％ 12％ 42％ 36％ 1％
Each component product property behind the hydrogenation fractionating
Project PAO-2 PAO-4 PAO-6
Kinematic viscosity, mm 2/s 40℃ 100℃ 7.41 2.26 18.73 4.03 36.98 6.48
Viscosity index 118 125 127
Condensation point, ℃ -61 -64 -60
Flash-point (opening), ℃ 178 214 232
The bromine valency, gBr/100g 0.015 0.015 0.015
Colorimetric, number ＜0.5 ＜0.5 ＜0.5
Carbon residue, % 0.008 0.012 0.013
Rotary oxygen bomb (150 ℃), min 435 430 448
Embodiment 3
By following processing condition, with C 8～13Alkene is raw material, with BF 3Amylalcohol promotor is that catalyzer carries out synthesizing poly alpha-olefin oil (PAO) experiment.
25 ℃ of polymerization temperatures
Reaction pressure 0.3Mpa
Reaction times 4h
Amylalcohol consumption 0.1%
BF 3Consumption 4%
60 ℃ of extraction temperatures
Refining time 0.5h
Carclazyte consumption 3% (stand oil relatively)
The oil product material balance sees the following form.
Material balance
Project Material balance
Raw material olefin, % 100
The refining oil that overlaps, % is wherein:＞280 ℃ of fraction＜280 ℃ fractions 95 86 9
Residue, % 3
Loss (containing clay dregs), % 3
The catalyst consumption amount, % 1
Oil property sees the following form.
＞280 ℃ of fraction character
Project Oil property
Kinematic viscosity, mm 2/s 40℃ 100℃ 20.14 4.03
Viscosity index 124
Flash-point (opening), ℃ 174
Condensation point, ℃ -62
Bromine number, gBr/100g 30.46
Carbon residue, % 0.034
Colorimetric 6.0
Rotary oxygen bomb (150 ℃), min 145
Oil product is as follows by material balance and oil property behind the following processing condition hydrogenation.
The hydrogenation technique condition
Catalyzer Temperature of reaction Reaction pressure Hydrogen-oil ratio Air speed
3996 270℃ 4.0MPa 500∶1 0.5h -1
Material balance behind the hydrogenation
＜280 ℃ of fractions PAO-2 PAO-4 PAO-6 Loss
9％ 10％ 44％ 36％ 1％
Each component product property behind the hydrogenation fractionating
Project PAO-2 PAO-4 PAO-6
Kinematic viscosity, mm 2/s 40℃ 100℃ 7.41 2.26 18.73 4.03 36.98 6.48
Viscosity index 118 125 127
Condensation point, ℃ -62 -64 -60
Flash-point (opening), ℃ 182 214 238
The bromine valency, gBr/100g 0.015 0.015 0.015
Colorimetric, number ＜0.5 ＜0.5 ＜0.5
Carbon residue, % 0.010 0.011 0.010
Rotary oxygen bomb (150 ℃), min 428 440 436

Claims (1)

1. the method for a synthesizing poly alpha-olefin oil, the employing boron trifluoride is a catalyzer, and alcohol is initiator, and waxcrack is a raw material, and described alcohol is methyl alcohol, ethanol, propyl alcohol, butanols or amylalcohol; It is characterized in that:
The weight ratio of initiator amount and raw material olefin is 0.01～1.0%
BF 3The weight ratio of consumption and raw material olefin is 1-5%
0～80 ℃ of temperature of reaction
Reaction pressure 0～1.0Mpa
Reaction times 1～6h;
Adopt two still parallel connections, evaporation-adsorb placed in-line operational path, raw material olefin is head tank in the Vehicle loaded pump feeder, and the head tank internal olefin is sent into reactor through feedstock pump, and initiator is pumped into reactor from the initiator jar through initiator simultaneously, fully stirs; Charge into BF 3Gas continues to stir, and keeps reaction pressure, and by circulating water cooling system, control reaction temperature, reaction times;
After reaction finishes, with BF residual in the reactor 3Gas is sent into the water-cooled jar, and by the heating to reactor, makes BF as much as possible 3Gas enters the water-cooled jar, cooled BF 3The compressed machine of gas enters second reactor of charging, fully stirs, and makes the residual BF of its absorption first reactor as much as possible 3Gas will cause a jar interior initiator then and be pumped into second reactor through initiator, charge into BF 3Gas carries out the reaction second time;
Stand oil in first reactor is pumped into the absorption still at the bottom of still, add 2～5% carclazyte, under 60 ℃ of conditions, fully stirs, and after 30 minutes material is sent into the product jar through filter.
CN2006100728743A 2006-04-14 2006-04-14 Method of synthesizing poly alpha-olefin oil Expired - Fee Related CN101054332B (en)

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Publication number Priority date Publication date Assignee Title
CN105693905B (en) * 2016-01-25 2017-11-17 沈阳市宏城精细化工厂 A kind of and highly miscible polyalphaolefin of Esters oil and its preparation method and application
CN108251155B (en) * 2016-12-28 2020-04-10 中国石油天然气股份有限公司 Preparation method of low-viscosity poly α -olefin synthetic oil
CN109593591B (en) * 2017-09-30 2022-05-17 中国石油化工股份有限公司 Low-viscosity poly-alpha-olefin lubricating oil base oil and preparation method and system thereof
CN111321002A (en) 2018-12-14 2020-06-23 中国石油天然气股份有限公司 Low-viscosity poly α -olefin lubricating oil and synthetic method thereof
CN114044731B (en) * 2021-12-06 2024-06-11 沈阳宏城精细化工科技有限公司 Alpha-olefin refined based on coal-to-olefin and application of alpha-olefin in preparation of poly alpha-olefin PAO oil

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