CN109593591A - Low viscosity poly alpha olefin lube base oil and preparation method thereof and system - Google Patents
Low viscosity poly alpha olefin lube base oil and preparation method thereof and system Download PDFInfo
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- CN109593591A CN109593591A CN201710938311.6A CN201710938311A CN109593591A CN 109593591 A CN109593591 A CN 109593591A CN 201710938311 A CN201710938311 A CN 201710938311A CN 109593591 A CN109593591 A CN 109593591A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
- C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
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Abstract
This disclosure relates to a kind of low viscosity poly alpha olefin lube base oil and preparation method thereof and system, this method comprises the following steps: (1) making the raw material containing alpha-olefin and contain BF3Catalyst and reaction promoter polymerization reaction is carried out in polymerizing reactor, obtain containing BF3The mix products of catalyst, reaction promoter and poly alpha olefin;(2) make the mix products be sent into heating in gas-liquid separation device to obtain mainly containing BF to carry out gas-liquid separation3The gas-phase product of catalyst and the liquid product for mainly containing poly alpha olefin;(3) at least part of the gas-phase product is returned in the polymerizing reactor.Disclosed method can prepare the poly alpha olefin of F content qualification and can continuously separate the BF in poly alpha olefin product3Catalyst without not generating waste water containing F in artificial interval batch turning and production process, and can recycle BF3Catalyst reduces catalyst waste.
Description
Technical field
This disclosure relates to the preparation field of lube base oil, and in particular, to a kind of low viscosity poly alpha olefin lubricating oil
Base oil and preparation method thereof and system.
Background technique
Lubricating oil specification is increasingly strict, and the demand of high-quality lubricating oil and synthetic oil rises appreciably, and poly alpha olefin is then
One of fastest-rising kind.It has operating temperature range wide, and low temperature, high-temperature stability are good, low pour point, low volatility, glues
The advantages that warm excellent performance, high antioxidant, high viscosity index (HVI), can be used on all kinds of high-grade machine oil of modulation, as gasoline engine oil,
Diesel engine oil, compressor oil, military lubricating oil etc..
Poly alpha olefin mainly carries out polymerization reaction by the alpha-olefin of C8-C12 under the action of catalyst, by separating, adds
The long chain alkane obtained after the processing of the series of process such as hydrogen.Poly alpha olefin dosage is maximum be at 100 DEG C viscosity be 4cSt and
6cSt, label PAO-4 and PAO-6.The linear paraffin skeleton of poly alpha olefin can guarantee good viscosity-temperature characteristics, shorter, more
Side chain be able to maintain low temperature flow again, in addition the groups such as aromatic-free, cycloalkane, be conducive to the stabilization of physics, chemistry.Cause
This, poly alpha olefin is a kind of ideal lube base oil.
The catalyst of low viscosity poly alpha olefin lubricating oil is with BF3Based on, Conventional process after the reaction was completed, need to be into
The processes such as row batch turning, displacement, alkali cleaning, washing can just completely remove F ion (1ppm or less), will generate largely contain F in the process
Ion waste water, and consume a large amount of BF3Catalyst.It needs to create matched waste water treatment plant containing F ion in this way, increases environmental protection
Pressure;And catalyst can not recycle after alkali cleaning washing, increase operating cost;If alkali cleaning, water washing tank are intermittently operated, also
Cost of labor is increased, there is production hidden danger.
Summary of the invention
Purpose of this disclosure is to provide a kind of method and system for preparing low viscosity poly alpha olefin lube base oil, the party
Method and system can reduce the pollution generated in the preparation of poly alpha olefin lube base oil, and improve production efficiency.
Another object of the present disclosure is to provide the low viscosity poly alpha olefin lube base oil of above method preparation.
To achieve the goals above, the first aspect of the disclosure, which provides, a kind of prepares low viscosity poly alpha olefin lube base
The method of oil, this method comprises the following steps: (1) making the raw material containing alpha-olefin and contain BF3Catalyst and reaction promoter
Polymerization reaction is carried out in polymerizing reactor, is obtained containing BF3The mix products of catalyst, reaction promoter and poly alpha olefin;
(2) make the mix products be sent into heating in gas-liquid separation device to obtain mainly containing BF to carry out gas-liquid separation3Catalyst
Gas-phase product and the liquid product for mainly containing poly alpha olefin;(3) make at least part of the gas-phase product back to institute
It states in polymerizing reactor.
Optionally, the gas-liquid separation device includes at least one of gas-liquid separation tower, knockout drum and heat exchanger.
Optionally, the gas-liquid separation tower is one of separation tower, normal pressure knockout tower and decompression separation tower, described
The number of plates of gas-liquid separation tower is 1~100 piece.
Optionally, the bottom temperature of the gas-liquid separation tower is 50~400 DEG C.
Optionally, the alpha-olefin raw material is the alpha-olefin of C6~C14.
Optionally, the reaction promoter be carbon atom number be 1~20 alcohol, carbon atom number be 1~20 ether, carbon atom number
For 1~20 carboxylic acid, carbon atom number be 1~20 ester and carbon atom number be 1~20 at least one of phenol.
Optionally, it is -50 to 100 DEG C that the condition of the polymerization reaction, which includes: reaction temperature,;Reaction pressure be 10Pa~
5MPa;The alpha-olefin raw material, the BF3The molar ratio of catalyst and the reaction promoter is 1:(0.001~0.2):
(0.001~0.4).
Optionally, this method further include: the F constituent content in liquid product described in on-line measurement;When the F constituent content
When higher than limit standard, so that at least part of the liquid product is back to the gas-liquid separation device and carry out the gas-liquid point
From, and the separation temperature of the gas-liquid separation device is adjusted if necessary;When the F constituent content is no more than the limit standard
When, the liquid product is directly subjected to the hydrotreating.
Optionally, the limit standard is that F constituent content is not more than 100ppm.
Optionally, this method further include: change the gas-phase product in First Heat Exchanger with the mix products
Heat is cooling, obtains the first heat exchange product containing gas phase and liquid phase;Make at least one of the gas phase in the first heat exchange product
Point back in the polymerizing reactor, and optionally make another part of gas phase in the first heat exchange product as tail
Gas discharge;The liquid phase in the first heat exchange product is set to be back to the gas through reflux unit with 0.1~50 mass reflux ratio
Liquid separating apparatus.
Optionally, this method further include: cool down the first heat exchange product further, obtain containing gas phase and liquid phase
Cooled product;Return at least part of the gas phase in the cooled product in the polymerizing reactor, and optionally
Another part of the gas phase in the cooled product is discharged as tail gas;Make the liquid phase in the cooled product through reflux unit
The gas-liquid separation device is back to 0.1~50 mass reflux ratio.
Optionally, this method further include: a part of the liquid phase in reflux unit is discharged from the reflux unit.
Optionally, this method further include: make at least part of the liquid product it is heated after enter hydrogenation system into
Row hydrotreating obtains the hydrogenation products of lube base oil head product as described in of olefin(e) centent reduction.
Optionally, this method further include: change the hydrogenation products with the liquid product in the second heat exchanger
Heat treatment.
Poly- α-the alkene of low viscosity that the method for the first aspect by the disclosure that the second aspect of the disclosure provides is prepared
Hydrocarbon lube base oil.
The third aspect of the disclosure provides a kind of system for preparing low viscosity poly alpha olefin lube base oil, the system packet
Include feed inlet, polymerizing reactor, gas-liquid separation device and discharge port;The feed inlet is reacted with the polymerizing reactor
The connection of object entrance, the product exit of the polymerizing reactor are connected to the entrance of the gas-liquid separation device, the gas-liquid point
It is connected to from the liquid outlet of device with the discharge port, the gas vent of the gas-liquid separation device and the polymerizing reactor
Reactant entrance connection.
Optionally, the gas-liquid separation device includes at least one of gas-liquid separation tower, knockout drum and heat exchanger.
Optionally, the gas-liquid separation tower is one of separation tower, normal pressure knockout tower and decompression separation tower, described
The number of plates of gas-liquid separation tower is 1~100 piece.
Optionally, which further includes the on-line measuring device for detecting impurity element in the heat transferring medium.
Optionally, which further includes First Heat Exchanger and reflux unit;The first entrance of the First Heat Exchanger and institute
State the gas vent connection of gas-liquid separation device, the product of the second entrance of the First Heat Exchanger and the polymerizing reactor
Outlet, the first outlet of the First Heat Exchanger are connected to the entrance of the reflux unit, and the of the First Heat Exchanger
Two outlets are connected to the entrance of the gas-liquid separation device, the liquid outlet of the reflux unit and the gas-liquid separation device
Entrance is connected to and optionally empties, and the gas vent of the reflux unit is connected to the reactant entrance of the polymerizing reactor
And it optionally empties.
Optionally, which further includes cooling device, the first outlet of the First Heat Exchanger and the cooling device
Entrance connection, the outlet of the cooling device is connected to the entrance of the reflux unit.
Optionally, which further includes hydrogenation plant, the liquid of the entrance of the hydrogenation plant and the gas-liquid separation device
Body outlet, the outlet of the hydrogenation plant are connected to the discharge port.
Optionally, which further includes the second heat exchanger, the first entrance of second heat exchanger and the hydrogenation plant
Outlet, the second entrance of second heat exchanger is connected to the liquid outlet of the gas-liquid separation device, described second
The first outlet of heat exchanger is connected to the discharge port, the second outlet of second heat exchanger and the entrance of the hydrogenation plant
It is connected to and is optionally connected to the entrance of the gas-liquid separation device.
Through the above technical solutions, the method for the preparation low viscosity poly alpha olefin lube base oil of the disclosure passes through in gas
Heating makes reaction promoter and BF in liquid separating apparatus3The complex depolymerization of formation, can prepare the poly alpha olefin of F content qualification and
The BF in poly alpha olefin product can continuously be separated3Catalyst is not necessarily to artificial interval batch turning, it is hidden to considerably reduce production safety
Suffer from;This method and system can make poly alpha olefin product and BF3Catalyst is completely separated, and is not generated in production process useless containing F
Water, and BF can be recycled3Catalyst reduces catalyst waste.The poly alpha olefin lube base prepared using this method
Oil viscosity is low and F constituent content is lower.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Attached drawing is and to constitute part of specification for providing further understanding of the disclosure, with following tool
Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings:
Fig. 1 is a kind of specific embodiment of the method for the preparation low viscosity poly alpha olefin lube base oil of the disclosure
Process flow chart.
Description of symbols
1 contains BF3Raw material of the catalyst 2 containing alpha-olefin
3 reaction promoter, 4 polymerizing reactor
5 gas-liquid separation tower, 6 First Heat Exchanger
7 cooler, 8 return tank
9 heating furnace, 10 hydrogenation system
11 compressor, 12 second heat exchanger
Specific embodiment
It is described in detail below in conjunction with specific embodiment of the attached drawing to the disclosure.It should be understood that this place is retouched
The specific embodiment stated is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of method for preparing low viscosity poly alpha olefin lube base oil, and this method includes following step
It is rapid: (1) to make the raw material containing alpha-olefin and contain BF3Catalyst and reaction promoter carry out polymerizeing in polymerizing reactor it is anti-
It answers, obtains containing BF3The mix products of catalyst, reaction promoter and poly alpha olefin;(2) mix products is made to be sent into gas-liquid separation dress
Middle heating is set to carry out gas-liquid separation, to mainly containing BF3The gas-phase product of catalyst and the liquid phase for mainly containing poly alpha olefin
Product;(3) at least part of gas-phase product is returned in polymerizing reactor.
The method of the preparation low viscosity poly alpha olefin lube base oil of the disclosure in gas-liquid separation device by heating
Make reaction promoter and BF3The complex depolymerization of formation can prepare the poly alpha olefin of F content qualification and can continuously separate poly- α-
BF in olefin product3Catalyst is not necessarily to artificial interval batch turning, considerably reduces production safety hidden danger;This method can make
Poly alpha olefin product and BF3Catalyst is completely separated, and does not generate waste water containing F in production process, and can recycle BF3It urges
Agent reduces catalyst waste.
According to the disclosure, gas-liquid separation device may include in gas-liquid separation tower, knockout drum and heat exchanger at least
One kind, preferably gas-liquid separation tower, in order to control separation operation condition, improve separative efficiency.
According to the disclosure, gas-liquid separation tower can be the knockout tower of this field conventional kind, the operation item of gas-liquid separation tower
Part can change in a big way, in order to guarantee gas-liquid separation efficiency, it is preferable that gas-liquid separation tower can be separation
One of tower, normal pressure knockout tower and decompression separation tower, preferably decompression separation tower;The number of plates of gas-liquid separation tower can be 1
~100 pieces, preferably 5~80 pieces;The bottom temperature of gas-liquid separation tower can be 50~400 DEG C, preferably 100~300 DEG C.
According to the disclosure, the reaction raw materials and catalyst that carry out alpha-olefine polymerizing can be the conventional kind of this field, α-
Olefin feedstock can be the alpha-olefin that carbon atom number is 6~14, for example, in 1- decene, 1- octene and 1- laurylene extremely
Few one kind;Reaction promoter can be carbon atom number be 1~20 alcohol, carbon atom number be 1~20 ether, carbon atom number be 1~20
Carboxylic acid, carbon atom number be 1~20 ester and carbon atom number be at least one of 1~20 phenol, preferably carbon atom number be 2
~8 alcohol;Contain BF3Catalyst in BF3Molar content can be 10%~100%, can also be containing a small amount of in catalyst
Inert component.
According to the disclosure, what the condition that alpha-olefin raw material carries out polymerization reaction can be conventional for this field, in order to further
Reaction conversion ratio is improved, the condition of polymerization reaction may include: that reaction temperature is -50 DEG C to 100 DEG C, preferably 0~80 DEG C;Instead
Answering pressure is 10Pa~5MPa, preferably 0.1~2MPa;Alpha-olefin raw material, BF3The molar ratio of catalyst and reaction promoter can be with
For 1:(0.001~0.2): (0.001~0.4), preferably 1:(0.005~0.1): (0.005~0.2).
According to the disclosure, in order to further increase gas-liquid separation efficiency, make full use of the heat in reaction system, this method
It can also include: that gas-phase product is made to carry out heat exchange cooling with mix products in First Heat Exchanger, obtain containing gas phase and liquid phase
First heat exchange product;Return at least part of the gas phase in the first heat exchange product in polymerizing reactor, in order to anti-
Only inert gas is accumulated, and another part of the gas phase in the first heat exchange product can optionally be discharged as tail gas;And it can be with
The liquid phase in the first heat exchange product is set to be back to gas-liquid separation device through reflux unit with 0.1~50 mass reflux ratio.Wherein,
Reflux unit can be return tank;First Heat Exchanger can be this field routine type and form, for example, plate heat exchanger,
Shell-and-tube heat exchanger etc., the disclosure does not do particular/special requirement;The mass reflux ratio of liquid phase in first heat exchange product can be further
Preferably 0.2~20.
Further, in order to improve the cooling effect of the first heat exchange product, this method may include: to make the first heat exchange product
It is further cooling, obtain the cooled product containing gas phase and liquid phase;Return at least part of the gas phase in cooled product
In polymerizing reactor, similarly, another part of the gas phase in the first heat exchange product can optionally be discharged as tail gas,
To prevent inert gas from accumulating;And the liquid phase in cooled product is made to be back to gas-liquid separation dress through return tank of top of the tower with 0.1~50
It sets, it is preferable that the mass reflux ratio of the liquid phase in cooled product can be 0.2~20.
In a kind of specific embodiment of the disclosure, this method may include: one for making liquid phase in reflux unit
Divide and be discharged from reflux unit, be preferably discharged the light component in liquid phase, to reduce the BF for being back to gas-liquid separation device3Catalysis
Dosage, to improve BF3The separative efficiency of catalyst and polymeric reaction product.
According to the disclosure, the liquid product containing poly alpha olefin can obtain poly alpha olefin by conventional post-processing step
Lube base oil, in a kind of specific embodiment of the disclosure, the liquid product containing poly alpha olefin can be passed through further
Obtain can be used as the alkane of lube base oil after hydrotreating, disclosed method can also include: to make liquid product
The heated rear hydrogenation system that enters carries out hydrotreating at least partially, and obtain olefin(e) centent reduction is used as lube base oil
The hydrogenation products of head product, the hydrogenation products further can obtain poly alpha olefin lube base oil through conventional treatment method.
The condition for wherein carrying out hydrotreating can be the popular response condition of this field, such as hydroconversion condition may include: reaction temperature
Degree is 200~400 DEG C, and preferably 220~380 DEG C, hydrogen partial pressure is 2~20MPa, preferably 5~15MPa, volume space velocity when liquid
It is 0.05~5 hour-1, preferably 0.1~3 hour-1, hydrogen to oil volume ratio is 200~1000 standard cubic meters/cubic meter, preferably
For 300~800 standard cubic meters/cubic meter.
Further, in order to improve the heat utilization ratios of hydrogenation products, this method may include: to make hydrogenation products second
Heat exchange processing is carried out with liquid product in heat exchanger, using the higher hydrogenation products of temperature as the heating of gas-liquid separation device
Heat source.
BF is improved according to the disclosure for the content of F element in real-time monitoring polymeric reaction product3Catalyst with polymerize
The separative efficiency of reaction product, this method can also include: the F constituent content in on-line measurement liquid product;When F constituent content
When higher than limit standard, so that at least part of liquid product is back to gas-liquid separation device and carry out gas-liquid separation;Wherein, it returns
Mass reflux ratio to the liquid product of gas-liquid separation device can be 0.1~50, preferably 0.2~20, larger when being adjusted to
Reflux ratio F constituent content still can not be made in liquid product to reach limit standard is point of adjustable gas-liquid separation device
From temperature;When F constituent content is no more than limit standard, liquid product directly can be subjected to hydrotreating.
Wherein, the limit standard of F constituent content can require to be defined according to lube product in liquid product, such as
Limit standard can be not more than 100ppm, preferably not greater than 10ppm for F constituent content.
It should be noted that such as without special requirement, hydrogenation catalyst used by method of the invention, hydrogenation plant and poly-
Closing reaction unit can according to need using the conventional use of catalyst of this field institute and device.For example, hydrogenation catalyst can
Think metallic catalyst, metal oxide, sulfide or the complex catalyst etc. of transition metal element, hydrogenation plant and polymerization are anti-
Answering device can be fixed bed, slurry bed system, tubular reactor etc..
The second aspect of the disclosure provides the low viscosity poly alpha olefin profit according to the preparation of the method for the first aspect of the disclosure
Lubricant base oil.F constituent content in the poly alpha olefin lube base oil is lower.
The third aspect of the disclosure provides a kind of system for preparing low viscosity poly alpha olefin lube base oil, such as Fig. 1 institute
Show, which includes feed inlet, polymerizing reactor 4, gas-liquid separation device 5 and discharge port;Feed inlet and polymerizing reactor 4
Reactant entrance connection, the product exit of polymerizing reactor 4 is connected to the entrance of gas-liquid separation device 5, and gas-liquid separation fills
It sets 5 liquid outlet to be connected to discharge port, the gas vent of gas-liquid separation device 5 and the reactant entrance of polymerizing reactor 4
Connection.
According to the disclosure, gas-liquid separation device 5 may include in gas-liquid separation tower, knockout drum and heat exchanger at least
One kind, preferably gas-liquid separation tower.Gas-liquid separation tower can be one in separation tower, normal pressure knockout tower and decompression separation tower
Kind, preferably decompression separation tower, the number of plates of gas-liquid separation tower can be 1~100 piece, preferably 5~80 pieces.
Further, in order to reduce the content of impurity element in product to guarantee product quality, which can also include
For detecting the on-line measuring device of impurity element in heat transferring medium.
In order to further increase gas-liquid separation efficiency, in a kind of specific embodiment of the disclosure, as shown in Figure 1, should
System can also include First Heat Exchanger 6 and reflux unit 8;The first entrance of First Heat Exchanger 6 can be with gas-liquid separation device 5
Gas vent connection, the second entrance of First Heat Exchanger 6 can be connected to the product exit of polymerizing reactor 4, and first changes
The first outlet of hot device 6 can be connected to the entrance of reflux unit 8, and the second outlet of First Heat Exchanger 6 can be with gas-liquid separation
The entrance of device 5 is connected to, and the liquid outlet of reflux unit 8 can be connected to the entrance of gas-liquid separation device 5 and optionally empty,
To be discharged inert gas, the gas vent of reflux unit 8 can be connected to and optionally with the reactant entrance of polymerizing reactor 4
Emptying.
In this case, in order to further increase gas-liquid separation efficiency, which can also include cooling device, at this time
The first outlet of First Heat Exchanger 6 can be connected to the entrance of cooling device, and the outlet of cooling device can be with reflux unit 8
Entrance connection.
According to the disclosure, the product liquid of gas-liquid separation device further can be added hydrogen to obtain lube base oil primiparity
Product, in a kind of specific embodiment of the disclosure, which can also include hydrogenation plant 10, and the entrance of hydrogenation plant 10 can
To be connected to the liquid outlet of gas-liquid separation device 5, the outlet of hydrogenation plant 10 can be connected to discharge port.
Further, in order to improve the heating efficiency of system, which can also include the second heat exchanger 12, and second
The first entrance of heat exchanger 12 can be with the outlet of hydrogenation plant 10, and the second entrance of the second heat exchanger 12 can be with gas-liquid
The liquid outlet of separator 5 is connected to, and the first outlet of the second heat exchanger 12 can be connected to discharge port, the second heat exchanger 12
Second outlet can be connected to the entrance of hydrogenation plant 10 and optionally be connected to the entrance of gas-liquid separation device 5.
In the disclosure preferably a kind of specific embodiment, gas-liquid separation device can be gas-liquid separation tower, the gas-liquid
Knockout tower can have multiple entrances, and for example including feed inlet, overhead reflux entrance and tower bottom reflux inlet, what it is in the disclosure is
In the case that system includes First Heat Exchanger 6 and reflux unit 8, the liquid outlet of reflux unit 8 can be with the tower of gas-liquid separation tower
Top reflux inlet is connected to and optionally empties, which can further increase the efficiency of gas-liquid separation;In this public affairs
In the case that the system opened includes hydrogenation plant 10 and the second heat exchanger 12, the second outlet of the second heat exchanger 12 can with add hydrogen
The entrance of device 10 is connected to and is optionally connected to the tower bottom reflux inlet of the gas-liquid separation tower, and the product of hydrogenation plant can at this time
For use as the heat source of gas-liquid separation tower tower reactor, the capacity usage ratio of system is improved.
The present invention will be further illustrated by embodiment below, but the present invention is not therefore subject to any restriction.
Instrument, device and reagent used by the embodiment of the present invention, unless otherwise instructed, be the instrument of this field routine, device and
Reagent, wherein BF3The separation rate of catalyst is defined as: BF in top gaseous phase product3Quality/catalyst charge in contain BF3
Quality × 100%.
Embodiment 1
As shown in Figure 1, being used as gas-liquid separation device, the raw material containing alpha-olefin using gas-liquid separation tower 1 in the present embodiment
For 1- decene, contain BF3Catalyst in BF3Content is 90%, and reaction promoter is 1- octanol, online using combustion ion chromatography
Measure the F content of tower bottom liquid product (specific method refers to ASTM D7359).
Make alpha-olefin raw material 1- decene, contain BF3Catalyst, recycling catalyst and reaction promoter 1- octanol enter polymerization
Polymerization reaction is carried out in reaction unit 4, reaction temperature is 25 DEG C;Reaction pressure is 0.15MPa;Raw material, BF containing alpha-olefin3
The molar ratio of catalyst and 1- octanol is 1:0.01:0.01, is obtained containing BF3The mixing of catalyst, 1- octanol and poly- 1- decene
Product enters mix products in gas-liquid separation tower 5 (8 pieces of the number of plates, 220 DEG C of bottom temperature) and heats to carry out gas-liquid separation,
It is respectively obtained from tower top and tower bottom and mainly contains BF3The top gaseous phase product of catalyst and reaction promoter and mainly contain poly- α-alkene
The tower bottom liquid product of hydrocarbon;
So that top gaseous phase product is carried out heat exchange cooling with mix products in First Heat Exchanger 6, obtains the first heat exchange product
Into further cooling down in cooler 7, the cooled product containing gas phase and liquid phase is obtained;Make gas phase in cooled product at least
A part returns in polymerizing reactor 4 through return tank 8, again after the compression of compressor 11, and rest part gas phase is as tail gas
It is discharged, the liquid phase in cooled product is back to gas-liquid separation tower 5, not timing discharge through return tank of top of the tower 8 with 1 mass reflux ratio
Liquid phase light component in return tank 8.
Tower bottom liquid product on-line measurement F content beats tower bottom liquid product all again if F content is greater than 10ppm
Enter 5 entrance of gas-liquid separation tower to be separated, if F content is not more than 10ppm, tower bottom liquid product is as qualified material into through adding
Hot stove 9 enters hydrogenation system 10 and carries out hydrotreating after heating, the condition of hydrotreating is entrance hydrogen partial pressure 10MPa, reaction temperature
270 DEG C of degree, volume space velocity 0.8h-1, hydrogen to oil volume ratio 700, hydrogenation products are as heat source the second heat exchanger 12 of feeding and gas
The heat exchange of 5 tower bottoms of liquid knockout tower.
According to the method for the present embodiment, after stable operation, the treating capacity that mix products enter gas-liquid separation tower is 1kg/h,
BF in mix products3The separation rate of catalyst is 100%, and the F content in hydrogenation products is 0ppm.
Embodiment 2
It is handled according to the method for embodiment 1, unlike, the top gaseous phase product of gas-liquid separation tower 5 is without first
Heat exchanger 6 and cooler 7, are returned directly in polymerizing reactor.
According to the method for the present embodiment, after stable operation, the treating capacity that mix products enter gas-liquid separation tower is 1kg/h,
BF in mix products3The separation rate of catalyst is 99.99%, and the F content in hydrogenation products is 2ppm.
Comparative example 1
It is handled according to the method for embodiment 1, unlike, the mix products of polymerization reaction use alkali cleaning, WATER-WASHING METHOD
Separate poly alpha olefin and BF3Catalyst specifically refers to.
According to the method for this comparative example, after stable operation, the treating capacity that mix products enter gas-liquid separation tower is 1kg/h,
BF in mix products3The separation rate of catalyst is 99.999%, and the F content in hydrogenation products is 10ppm.
From the data of embodiment 1-2 and comparative example 1 as it can be seen that disclosed method can be realized alpha-olefin polymerization product
And BF3The continuous effective of catalyst separates, and is not necessarily to artificial interval batch turning, fast to the processing speed of mix products, polymerizate F contains
It measures up to standard and does not generate waste water containing F.Also, polymerizing reactor is returned to after exchanging heat in gas-liquid separation tower top gaseous phase product
In, and tower bottom liquid product on-line monitoring F content make unqualified tower bottom liquid phase product reflux in the case where, can further increase
BF3The separation rate and polymeric reaction product quality of catalyst.
The preferred embodiment of the disclosure is described in detail in conjunction with attached drawing above, still, the disclosure is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure
Monotropic type, these simple variants belong to the protection scope of the disclosure
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (23)
1. a kind of method for preparing low viscosity poly alpha olefin lube base oil, which is characterized in that this method comprises the following steps:
(1) make the raw material containing alpha-olefin and contain BF3Catalyst and reaction promoter carry out polymerizeing in polymerizing reactor it is anti-
It answers, obtains containing BF3The mix products of catalyst, reaction promoter and poly alpha olefin;
(2) make the mix products be sent into heating in gas-liquid separation device to obtain mainly containing BF to carry out gas-liquid separation3Catalysis
The gas-phase product of agent and the liquid product for mainly containing poly alpha olefin;With
(3) at least part of the gas-phase product is returned in the polymerizing reactor.
2. the method according to claim 1, wherein the gas-liquid separation device includes gas-liquid separation tower, gas-liquid
At least one of knockout drum and heat exchanger.
3. according to the method described in claim 2, it is characterized in that, the gas-liquid separation tower is separation tower, normal pressure separation
One of tower and decompression separation tower, the number of plates of the gas-liquid separation tower are 1~100 piece.
4. according to the method described in claim 2, it is characterized in that, the bottom temperature of the gas-liquid separation tower is 50~400 DEG C.
5. the method according to claim 1, wherein the alpha-olefin raw material is the alpha-olefin of C6~C14.
6. the method according to claim 1, wherein the reaction promoter be carbon atom number be 1~20 alcohol, carbon
The ester and carbon atom number that carboxylic acid that ether that atomicity is 1~20, carbon atom number are 1~20, carbon atom number are 1~20 are 1~20
At least one of phenol.
7. the method according to claim 1, wherein it is -50 that the condition of the polymerization reaction, which includes: reaction temperature,
DEG C to 100 DEG C;Reaction pressure is 10Pa~5MPa;The alpha-olefin raw material, the BF3Catalyst and the reaction promoter rub
You are than being 1:(0.001~0.2): (0.001~0.4).
8. the method according to claim 1, wherein this method further include:
F constituent content in liquid product described in on-line measurement;
When the F constituent content is higher than limit standard, at least part of the liquid product is made to be back to the gas-liquid point
The gas-liquid separation is carried out from device, and adjusts the separation temperature of the gas-liquid separation device if necessary;
When the F constituent content is no more than the limit standard, the liquid product is directly subjected to the hydrotreating.
9. according to the method described in claim 8, it is characterized in that, the limit standard is that F constituent content is not more than 100ppm.
10. the method according to claim 1, wherein this method further include:
So that the gas-phase product is exchanged heat in First Heat Exchanger with the mix products, obtains containing gas phase and liquid phase
One heat exchange product;
It returns at least part of the gas phase in the first heat exchange product in the polymerizing reactor, and optionally makes
Another part of gas phase in the first heat exchange product is discharged as tail gas;Pass through back the liquid phase in the first heat exchange product
It flows device and the gas-liquid separation device is back to 0.1~50 mass reflux ratio.
11. according to the method described in claim 10, it is characterized in that, this method further include:
It cools down the first heat exchange product further, obtains the cooled product containing gas phase and liquid phase;
It returns at least part of the gas phase in the cooled product in the polymerizing reactor, and optionally makes described
Another part of gas phase in cooled product is discharged as tail gas;Make the liquid phase in the cooled product through reflux unit with 0.1
~50 mass reflux ratio is back to the gas-liquid separation device.
12. method described in 0 or 11 according to claim 1, which is characterized in that this method further include: make the liquid in reflux unit
A part of phase is discharged from the reflux unit.
13. the method according to claim 1, wherein this method further include: make at least the one of the liquid product
Enter hydrogenation system after part is heated and carry out hydrotreating, at the beginning of obtaining lube base oil described in the conduct of olefin(e) centent reduction
The hydrogenation products of product.
14. according to the method for claim 13, which is characterized in that this method further include: make the hydrogenation products second
Heat exchange processing is carried out with the liquid product in heat exchanger.
15. the low viscosity poly alpha olefin lube base oil that method described in any one of claim 1~14 is prepared.
16. a kind of system for preparing low viscosity poly alpha olefin lube base oil, which is characterized in that the system include feed inlet,
Polymerizing reactor, gas-liquid separation device and discharge port;The reactant entrance of the feed inlet and the polymerizing reactor connects
Logical, the product exit of the polymerizing reactor is connected to the entrance of the gas-liquid separation device, the gas-liquid separation device
Liquid outlet is connected to the discharge port, the reactant of the gas vent of the gas-liquid separation device and the polymerizing reactor
Entrance connection.
17. system according to claim 16, which is characterized in that the gas-liquid separation device includes gas-liquid separation tower, gas
At least one of liquid knockout drum and heat exchanger.
18. system according to claim 17, which is characterized in that the gas-liquid separation tower is separation tower, normal pressure point
From one of tower and decompression separation tower, the number of plates of the gas-liquid separation tower is 1~100 piece.
19. system according to claim 16, which is characterized in that the system further includes for detecting in the heat transferring medium
The on-line measuring device of impurity element.
20. system according to claim 16, which is characterized in that the system further includes First Heat Exchanger and reflux unit;
The first entrance of the First Heat Exchanger is connected to the gas vent of the gas-liquid separation device, and the second of the First Heat Exchanger
Entrance is connected to the product exit of the polymerizing reactor, the first outlet of the First Heat Exchanger and the reflux unit
Entrance connection, the second outlet of the First Heat Exchanger are connected to the entrance of the gas-liquid separation device, the reflux unit
Liquid outlet is connected to the entrance of the gas-liquid separation device and optionally empties, the gas vent of the reflux unit with it is described
The reactant entrance of polymerizing reactor is connected to and optionally empties.
21. system according to claim 20, which is characterized in that the system further includes cooling device, first heat exchange
The first outlet of device is connected to the entrance of the cooling device, and the outlet of the cooling device connects with the entrance of the reflux unit
It is logical.
22. system according to claim 16, which is characterized in that the system further includes hydrogenation plant, the hydrogenation plant
Entrance be connected to the liquid outlet of the gas-liquid separation device, the outlet of the hydrogenation plant is connected to the discharge port.
23. system according to claim 22, which is characterized in that the system further includes the second heat exchanger, and described second changes
The outlet of the first entrance of hot device and the hydrogenation plant, the second entrance and the gas-liquid separation of second heat exchanger
The liquid outlet of device is connected to, and the first outlet of second heat exchanger is connected to the discharge port, second heat exchanger
Second outlet is connected to the entrance of the hydrogenation plant and is optionally connected to the entrance of the gas-liquid separation device.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113522191A (en) * | 2020-04-20 | 2021-10-22 | 中国石油化工股份有限公司 | Apparatus and method for producing polyalphaolefins |
CN115010568A (en) * | 2021-03-05 | 2022-09-06 | 中国石化工程建设有限公司 | System and method for continuously producing poly alpha-olefin |
RU2808167C1 (en) * | 2020-04-20 | 2023-11-24 | Чайна Петролеум Энд Кемикал Корпорейшн | Installation and method for obtaining polyalphaolefins |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5705727A (en) * | 1995-06-13 | 1998-01-06 | Amoco Corporation | BF3 recovery process |
US5811616A (en) * | 1995-06-13 | 1998-09-22 | Amoco Corporation | BF3 gas recovery process |
CN1289344A (en) * | 1998-10-29 | 2001-03-28 | 日本石油化学株式会社 | Method of removing and recovering boron trifluoride with metal fluoride and process for polyolefin production using the same |
WO2005023419A1 (en) * | 2003-09-03 | 2005-03-17 | Exxonmobil Chemical Patents Inc. | Catalyst recovery process |
CN101054332A (en) * | 2006-04-14 | 2007-10-17 | 中国石油抚顺石油化工公司 | Method of synthesizing poly alpha-olefin oil |
CN102807640A (en) * | 2011-06-02 | 2012-12-05 | 北京化工大学 | Initiation system based on boron trifluoride and method for preparing polyisobutylene using initiation system |
CN103387628A (en) * | 2012-05-07 | 2013-11-13 | 中国石油化工股份有限公司 | Alkene polymerization system and method |
CN104560191A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of low-viscosity base oil of lubricating oil |
-
2017
- 2017-09-30 CN CN201710938311.6A patent/CN109593591B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5705727A (en) * | 1995-06-13 | 1998-01-06 | Amoco Corporation | BF3 recovery process |
US5811616A (en) * | 1995-06-13 | 1998-09-22 | Amoco Corporation | BF3 gas recovery process |
CN1289344A (en) * | 1998-10-29 | 2001-03-28 | 日本石油化学株式会社 | Method of removing and recovering boron trifluoride with metal fluoride and process for polyolefin production using the same |
WO2005023419A1 (en) * | 2003-09-03 | 2005-03-17 | Exxonmobil Chemical Patents Inc. | Catalyst recovery process |
CN101054332A (en) * | 2006-04-14 | 2007-10-17 | 中国石油抚顺石油化工公司 | Method of synthesizing poly alpha-olefin oil |
CN102807640A (en) * | 2011-06-02 | 2012-12-05 | 北京化工大学 | Initiation system based on boron trifluoride and method for preparing polyisobutylene using initiation system |
CN103387628A (en) * | 2012-05-07 | 2013-11-13 | 中国石油化工股份有限公司 | Alkene polymerization system and method |
CN104560191A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of low-viscosity base oil of lubricating oil |
Non-Patent Citations (1)
Title |
---|
张卫江等: "聚α-烯烃合成油制备过程中BF3络合物的分离及回收", 《化工进展》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113522191A (en) * | 2020-04-20 | 2021-10-22 | 中国石油化工股份有限公司 | Apparatus and method for producing polyalphaolefins |
RU2808167C1 (en) * | 2020-04-20 | 2023-11-24 | Чайна Петролеум Энд Кемикал Корпорейшн | Installation and method for obtaining polyalphaolefins |
CN115010568A (en) * | 2021-03-05 | 2022-09-06 | 中国石化工程建设有限公司 | System and method for continuously producing poly alpha-olefin |
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