CN108794670B - Improved process for synthesizing polyalphaolefin base oils - Google Patents
Improved process for synthesizing polyalphaolefin base oils Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 229920013639 polyalphaolefin Polymers 0.000 title claims abstract description 43
- 239000002199 base oil Substances 0.000 title claims abstract description 41
- 230000002194 synthesizing effect Effects 0.000 title claims description 15
- 239000003999 initiator Substances 0.000 claims abstract description 112
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 150000001336 alkenes Chemical class 0.000 claims abstract description 31
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 20
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 14
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 10
- 229940069096 dodecene Drugs 0.000 claims description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 229940095068 tetradecene Drugs 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims 4
- 239000003054 catalyst Substances 0.000 description 21
- 239000003513 alkali Substances 0.000 description 9
- 238000010538 cationic polymerization reaction Methods 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- -1 aluminum trichloride-2-ethyl hexanol Lewis acid Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polymerization Catalysts (AREA)
- Lubricants (AREA)
Abstract
The present invention provides an improved process for the synthesis of polyalphaolefin base oils, comprising the steps of: step 1, unifying the particle size of the initiator aluminum trichloride to any value in 100-400 μm; step 2, heating the raw material olefin to a target temperature of 100-120 ℃, then adding an initiator aluminum trichloride in a slow-release feeding mode, and obtaining poly-alpha-olefin base oil after the reaction is stable for 2-8 hours; the mass ratio of the total mass of the initiator aluminum trichloride to the raw material olefin is 1:20-1: 100; the slow release feeding mode is as follows: stage one, adding 10-20% of the total mass of the initiator at a constant speed within 30-50 minutes; stage two, adding 10-20% of the total mass of the initiator at constant speed for 50-70 minutes; stage three, adding 20-30% of the total mass of the initiator at constant speed within 30-50 minutes; and step four, adding 30-60 percent of the total mass of the initiator at constant speed within 20-40 minutes. The method of the invention not only can improve the risk of system temperature runaway caused by concentrated reaction heat release on operation, but also can improve the stability of product quality.
Description
Technical Field
The invention relates to the field of synthesis of base oil of poly-alpha-olefin synthetic oil, in particular to an improved process for initiating alpha-olefin polymerization by cations.
Background
There are two methods for producing lube base oil by using aluminium trichloride initiated alpha-olefin polymerization in industry:
the direct initiation process comprises the following steps: the catalyst is directly added to the raw materials, or the raw materials are quantitatively added to the initiator dispersed in the solvent.
The complex catalyst process comprises the following steps: complexing aluminum trichloride with alcohol, ether and ester complexing agent to form homogeneous catalyst, and regulating the adding speed of the complexing catalyst to control the reaction temperature.
US7550640 discloses that aluminum trichloride solid is used as an initiator, water is used as an accelerant, decene and dodecene are used as raw materials, and 40-100 mm of aluminum trichloride solid is synthesized2The high-viscosity poly alpha-olefin synthetic oil with the temperature of 100 ℃ per second has the advantages of long reaction time, difficult oil product treatment and low product yield, and the reaction temperature needs to be controlled between 45 ℃ below zero and 30 ℃ below zero.
CN1054986 discloses a novel aluminum trichloride-2-ethyl hexanol Lewis acid type liquid catalyst, which can effectively control side reaction in the reaction process, and adjust the dosage of the catalyst according to the measured polymerization activity of alpha-olefin to obtain poly alpha-olefin synthetic oil with high yield of low-viscosity oil.
US20070225534 discloses a poly-alpha-olefin synthetic oil with low viscosity and good low-temperature performance, which is synthesized by using aluminum trichloride solid as an initiator, acetic ester and normal alcohol as double accelerators and C6-C14 as raw materials.
The alcohol is utilized to complex the aluminum trichloride into the liquid catalyst, so that the adding amount of the catalyst can be effectively controlled, but after the alcohol is added, the acidity of the aluminum trichloride becomes weak, the sleep period is easy to overlong, the excessive adding of the catalyst is caused, the hidden danger of instantaneous temperature runaway still exists, in addition, the excessive adding of the alcohol also can cause more oil sludge after production, and extra burden is brought to the product aftertreatment. The storage and the transportation of the complex catalyst also have the hidden troubles of aluminum trichloride precipitation, pipeline corrosion, pipeline blockage and the like.
Disclosure of Invention
The main object of the present invention is to provide an improved method for synthesizing polyalphaolefin base oil, which can not only improve the risk of system temperature runaway caused by the concentration of reaction heat release on operation, but also improve the stability of product quality.
In order to achieve the above object, the present invention provides an improved method for synthesizing polyalphaolefin base oil, comprising the steps of:
step 1, unifying the particle size of the initiator aluminum trichloride to any value in 100-400 μm;
step 2, heating the raw material olefin to a target temperature of 100-120 ℃, then adding an initiator aluminum trichloride in a slow-release feeding mode, and obtaining poly-alpha-olefin base oil after the reaction is stable for 2-8 hours; the mass ratio of the total mass of the initiator aluminum trichloride to the raw material olefin is 1:20-1: 100;
the slow release feeding mode is as follows: stage one, adding 10-20% of the total mass of the initiator at a constant speed within 30-50 minutes; stage two, adding 10-20% of the total mass of the initiator at constant speed for 50-70 minutes; stage three, adding 20-30% of the total mass of the initiator at constant speed within 30-50 minutes; and step four, adding 30-60 percent of the total mass of the initiator at constant speed within 20-40 minutes.
In order to achieve the above objects, the present invention also provides another improved method for synthesizing polyalphaolefin base oil, comprising the steps of:
step 1, unifying the particle size of the initiator aluminum trichloride to any value in 100-400 μm;
step 2, heating the raw material olefin to a target temperature of 60-80 ℃, then adding an initiator aluminum trichloride in a slow-release feeding mode, and obtaining poly-alpha-olefin base oil after the reaction is stable for 2-8 h; the mass ratio of the total mass of the initiator aluminum trichloride to the raw material olefin is 1:20-1: 100;
the slow release feeding mode is as follows: stage one, adding 10-20% of the total mass of the initiator at a constant speed within 30-50 minutes; stage two, 20-30% of the total mass of the initiator is added at a constant speed within 50-70 minutes; stage three, adding 20-30% of the total mass of the initiator at constant speed within 30-50 minutes; and step four, adding 30-50% of the total mass of the initiator at constant speed within 20-40 minutes.
In order to achieve the above objects, the present invention also provides a third improved method for synthesizing polyalphaolefin base oil, comprising the steps of:
step 1, unifying the particle size of the initiator aluminum trichloride to any value in 100-400 μm;
step 2, heating the raw material olefin to a target temperature of 0-10 ℃, then adding an initiator aluminum trichloride in a slow-release feeding mode, and obtaining poly-alpha-olefin base oil after the reaction is stable for 2-8 hours; the mass ratio of the total mass of the initiator aluminum trichloride to the raw material olefin is 1:20-1: 100;
the slow release feeding mode is as follows: stage one, 30-50% of the total mass of the initiator is added at a constant speed for 60-80 minutes; and in the second stage, 50-70% of the total mass of the initiator is added at constant speed for 30-50 minutes.
In order to achieve the above objects, the present invention also provides a fourth improved method for synthesizing polyalphaolefin base oil, comprising the steps of:
step 1, unifying the particle size of the initiator aluminum trichloride to any value in 100-400 μm;
step 2, controlling the olefin as a raw material to a target temperature of 30-50 ℃, then adding an initiator aluminum trichloride in a slow-release feeding mode, and obtaining poly-alpha-olefin base oil after the reaction is stable for 2-8 hours; the mass ratio of the total mass of the initiator aluminum trichloride to the raw material olefin is 1:20-1: 100;
the slow release feeding mode is as follows: stage one, 30-40% of the total mass of the initiator is added at a constant speed within 30-50 minutes; stage two, 30-40% of the total mass of the initiator is added at constant speed for 50-70 minutes; and in the third stage, 20-30% of the total mass of the initiator is added at constant speed within 30-50 minutes.
The improved method for synthesizing the poly alpha-olefin base oil, provided by the invention, is characterized in that in the step 1, the particle size of the preferred unified initiator aluminum trichloride is one of 100 mu m, 200 mu m, 300 mu m and 400 mu m.
The improved method for synthesizing the polyalphaolefin base oil, provided by the invention, has the advantages that the initiator aluminum trichloride is uniform in particle size through a grinding and screening mode.
In the improved method for synthesizing the polyalphaolefin base oil, the raw olefin is preferably dehydrated by using a molecular sieve before being used, the water content is controlled to be below 20ppm, and the olefin is octene, decene, dodecene or tetradecene.
Compared with the prior art, the invention has the following advantages:
(1) after the particle size of the initiator is unified, the initiation rate difference caused by the difference of the specific surface areas of the aluminum trichloride can be avoided, the stability of the initiator is ensured, and the basic guarantee is provided for the process stability.
(2) By utilizing the initiator slow-release process, the reaction temperature can be controlled, temperature runaway caused by instant initiation of reaction can be effectively prevented, the reaction can be carried out more stably, and the stability of the product can be ensured.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The present invention provides an improved process for the synthesis of polyalphaolefin base oils comprising the steps of:
and grinding the aluminum trichloride under the anhydrous and oxygen-free conditions, and screening and collecting the aluminum trichloride by using a screen after grinding. Dehydrating raw material olefin, adding the dehydrated raw material olefin into a reaction bottle, heating the reaction raw material to a target reaction temperature by utilizing an oil bath, starting a feeder, and determining different initiator slow-release processes according to a target product to be synthesized.
The first step of the initiation process of the aluminum trichloride initiation system is that aluminum trichloride and water in reaction raw materials form an ion pair, the specific surface area of aluminum trichloride particles is an important factor for determining the formation of the ion pair, in order to avoid initiation rate difference caused by different specific surface areas of aluminum trichloride, the process requires that an initiator is pretreated, the particle size distribution of the used aluminum trichloride is uniformly and uniformly distributed, and the particle size distribution (97% of particle size) of the aluminum trichloride is ensured to be any value of 100-400 mu m, preferably any value of 100 mu m, 200 mu m, 300 mu m and 400 mu m.
The raw materials of octene, decene, dodecene or tetradecene need to be dehydrated by a molecular sieve before use, and the water content is controlled to be below 20 ppm.
According to the viscosity of a base oil product to be synthesized, before adding an initiator aluminum trichloride, the initial temperature of the raw material olefin is controlled to be 0-120 ℃, then different initiator slow-release processes are selected, the reaction temperature is stable, and after the aluminum trichloride is completely added, the reaction is continued for a period of time, so that the conversion rate is ensured.
The invention provides a cationic polymerization improved process, which is suitable for octene, decene, dodecene and tetradecene cationic polymerization initiated by aluminum trichloride, is different from the traditional cationic polymerization process, changes and unifies the particle size distribution of the aluminum trichloride, minimizes the influence of diffusion on the reaction, determines the temperature for adding an initiator according to the viscosity of a base oil product to be synthesized, and then ensures the reaction to be stably carried out by selecting a slow-release feeding mode to obtain a high-quality base oil product.
The slow release feeding mode 1 is as follows: stage one, adding 10-20% of the total mass of the initiator at a constant speed within 30-50 minutes; stage two, adding 10-20% of the total mass of the initiator at constant speed for 50-70 minutes; stage three, adding 20-30% of the total mass of the initiator at constant speed within 30-50 minutes; and step four, adding 30-60 percent of the total mass of the initiator at constant speed within 20-40 minutes.
The slow release feeding mode 2 comprises the following steps: stage one, adding 10-20% of the total mass of the initiator at a constant speed within 30-50 minutes; stage two, 20-30% of the total mass of the initiator is added at a constant speed within 50-70 minutes; stage three, adding 20-30% of the total mass of the initiator at constant speed within 30-50 minutes; and step four, adding 30-50% of the total mass of the initiator at constant speed within 20-40 minutes.
The slow release feeding mode 3 is as follows: stage one, 30-50% of the total mass of the initiator is added at a constant speed for 60-80 minutes; and in the second stage, 50-70% of the total mass of the initiator is added at constant speed for 30-50 minutes.
The slow release feeding mode is as follows: stage one, 30-40% of the total mass of the initiator is added at a constant speed within 30-50 minutes; stage two, 30-40% of the total mass of the initiator is added at constant speed for 50-70 minutes; and in the third stage, 20-30% of the total mass of the initiator is added at constant speed within 30-50 minutes.
The present invention will be described in detail below with reference to specific examples.
Example 1:
this example provides an improved process for aluminum trichloride-initiated cationic polymerization of decene, comprising the steps of:
adding 300ml of decene into a 500ml reaction bottle, putting the reaction bottle into an oil bath, setting the temperature of the oil bath to 120 ℃ after the temperature of the reaction bottle rises to 120 ℃, and adding aluminum trichloride into the reaction in four stages by adopting a slow release process 1: stage 1, 20% of the total amount of initiator is added within 30 minutes; stage 2, 20% of the total amount of the initiator is added within 50 minutes; stage 3, 20% of the total amount of the initiator is added within 30 minutes; in stage 4, 40% of the total initiator was added over 20 minutes. The particle size of the catalyst is controlled to be 200 mu m, the total adding amount of the catalyst is 3.7g, the temperature is stable in the whole slow release process, and the temperature rise range is within 5 ℃. And after the reaction is continued for 1 hour, the product is washed by alkali and cut to obtain the product.
Example 2:
this example provides an improved process for aluminum trichloride-initiated cationic polymerization of decene, comprising the steps of:
adding 300ml of decene into a 500ml reaction bottle, putting the reaction bottle into an oil bath, setting the temperature of the oil bath to 60 ℃ after the temperature of the reaction bottle rises to 60 ℃, and adding aluminum trichloride into the reaction in four stages by adopting a slow release process 2: stage 1, 20% of the total amount of initiator is added within 30 minutes; stage 2, 20% of the total amount of the initiator is added within 50 minutes; stage 3, 30 percent of the total amount of the initiator is added within 30 minutes; stage 4, 30% of the total amount of initiator was added over 20 minutes. The particle size of the catalyst is controlled to be 200 mu m, the total adding amount of the catalyst is 4.4g, the temperature is stable in the whole slow release process, and the temperature rise range is within 5 ℃. And after the reaction is continued for 1 hour, the product is washed by alkali and cut to obtain the product.
Example 3:
this example provides an improved process for aluminum trichloride-initiated cationic polymerization of decene, comprising the steps of:
adding 300ml of decene into a 500ml reaction bottle, putting the reaction bottle into an oil bath, setting the temperature of the oil bath to 40 ℃ after the temperature of the reaction bottle rises to 40 ℃, and adding aluminum trichloride into the reaction in three stages by adopting a slow release process 4: stage 1, 30 percent of the total amount of the initiator is added within 30 minutes; stage 2, 40% of the total amount of the initiator is added within 50 minutes; stage 3, 30% of the total initiator was added over 30 minutes. The particle size of the catalyst is controlled to be 200 mu m, the total adding amount of the catalyst is 5.5g, the temperature is stable in the whole slow release process, and the temperature rise range is within 5 ℃. And after the reaction is continued for 1.5 hours, the product is washed by alkali and cut to obtain the product.
Example 4:
this example provides an improved process for aluminum trichloride-initiated cationic polymerization of decene, comprising the steps of:
adding 200ml of decene and 100ml of heptane into a 500ml reaction bottle, placing the reaction bottle into a cold bath, setting the temperature of the cold bath to 5 ℃ after the temperature of liquid reaches 5 ℃, and adding aluminum trichloride into the reaction in two stages by adopting a slow release process 3: stage 1, 40% of the total amount of initiator is added within 60 minutes; stage 2, 60% of the total amount of initiator was added over 30 minutes. The particle size of the catalyst is controlled to be 100 mu m, the total adding amount of the catalyst is 6.6g, the temperature is stable in the whole slow release process, and the temperature rise range is within 5 ℃. And after the reaction is continued for 2 hours, the product is washed by alkali and cut to obtain the product.
Example 5:
this example provides an improved process for aluminum trichloride initiated cationic polymerization of octene, comprising the steps of:
adding 300ml of octene into a 500ml reaction bottle, putting the reaction bottle into an oil bath, setting the temperature of the oil bath to 105 ℃ after the temperature of the reaction bottle rises to 105 ℃, and adding aluminum trichloride into the reaction in four stages by adopting a slow release process 1: stage 1, 20% of the total amount of initiator is added within 30 minutes; stage 2, 20% of the total amount of the initiator is added within 50 minutes; stage 3, 20% of the total amount of the initiator is added within 30 minutes; in stage 4, 40% of the total initiator was added over 20 minutes. The particle size of the catalyst is controlled to be 300 mu m, the total adding amount of the catalyst is 3.7g, the temperature is stable in the whole slow release process, and the temperature rise range is within 5 ℃. And after the reaction is continued for 1 hour, the product is washed by alkali and cut to obtain the product.
Example 6:
this example provides an improved process for aluminum trichloride-initiated dodecene cationic polymerization, comprising the steps of:
adding 300ml of dodecene into a 500ml reaction bottle, putting the reaction bottle into an oil bath, setting the temperature of the oil bath to 80 ℃ after the temperature of the reaction bottle rises to 80 ℃, and adding aluminum trichloride into the reaction in four stages by adopting a slow release process 1: stage 1, 20% of the total amount of initiator is added within 30 minutes; stage 2, 20% of the total amount of the initiator is added within 50 minutes; stage 3, 20% of the total amount of the initiator is added within 30 minutes; in stage 4, 40% of the total initiator was added over 20 minutes. The particle size of the catalyst is controlled to be 100 mu m, the total adding amount of the catalyst is 4.4g, the temperature is stable in the whole slow release process, and the temperature rise range is within 5 ℃. And after the reaction is continued for 1 hour, the product is washed by alkali and cut to obtain the product.
The process of the invention is illustrated in detail by 4 sets of comparative proportional examples.
Comparative example 1:
adding 300ml of decene into a 500ml reaction bottle, adding 4.5g of aluminum trichloride at room temperature, reacting at the temperature of 180 ℃ instantly, stabilizing the reaction at 110 ℃, continuing to react for 3 hours, washing the product with alkali, and cutting to obtain the product.
Comparative example 2:
adding 300ml of decene into a 500ml reaction bottle, adding 4.5g of aluminum trichloride at room temperature, reacting at 150 ℃ after instant initiation, stabilizing the reaction at 80 ℃, continuing to react for 3 hours, washing the product with alkali, and cutting to obtain the product.
Comparative example 3:
adding 300ml of decene into a 500ml reaction bottle, adding 4.5g of aluminum trichloride at room temperature, reacting at 100 ℃ after instant initiation, stabilizing the reaction at 40 ℃, continuing to react for 3 hours, washing the product with alkali, and cutting to obtain the product.
Comparative example 4:
adding 100ml of heptane into a 500ml reaction bottle, adding 4.5g of aluminum trichloride at room temperature, stirring for 15min until the aluminum trichloride is completely dispersed in the solvent, and stirring well, stabilizing the suspension at 10 ℃, slowly adding decene, reacting for 10 hours at 15 ℃, then carrying out alkaline washing on the product, and cutting to obtain the product.
The indices of the products obtained in examples 1 to 4 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1 indices of the products of the examples and comparative examples
Compared with PAO products synthesized by the original process (comparative examples 1-4), the PAO products synthesized by the optimized process (examples 1-4) have higher viscosity index and lower low-temperature pour point performance of oil products with the same viscosity.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (16)
1. An improved process for synthesizing a polyalphaolefin base oil, comprising the steps of:
step 1, unifying the particle size of the initiator aluminum trichloride to any value in 100-400 μm;
step 2, heating the raw material olefin to a target temperature of 100-120 ℃, then adding an initiator aluminum trichloride in a slow-release feeding mode, and obtaining poly-alpha-olefin base oil after the reaction is stable for 2-8 hours; the mass ratio of the total mass of the initiator aluminum trichloride to the raw material olefin is 1:20-1: 100;
the slow release feeding mode is as follows: stage one, adding 10-20% of the total mass of the initiator at a constant speed within 30-50 minutes; stage two, adding 10-20% of the total mass of the initiator at constant speed for 50-70 minutes; stage three, adding 20-30% of the total mass of the initiator at constant speed within 30-50 minutes; and step four, adding 30-60 percent of the total mass of the initiator at constant speed within 20-40 minutes.
2. The improved process for the synthesis of polyalphaolefin base oils of claim 1, wherein in step 1, the unified initiator aluminum trichloride has a particle size of one of 100 μm, 200 μm, 300 μm, and 400 μm.
3. The improved process for the synthesis of polyalphaolefin base oils of claim 1, wherein the initiator aluminum trichloride is sized uniformly by means of grinding and sieving.
4. The improved process for the synthesis of polyalphaolefin base oils according to claim 1, wherein the olefin feedstock is dehydrated by molecular sieves before use, the water content is controlled to be less than 20ppm, and the olefin is octene, decene, dodecene or tetradecene.
5. An improved process for synthesizing a polyalphaolefin base oil, comprising the steps of:
step 1, unifying the particle size of the initiator aluminum trichloride to any value in 100-400 μm;
step 2, heating the raw material olefin to a target temperature of 60-80 ℃, then adding an initiator aluminum trichloride in a slow-release feeding mode, and obtaining poly-alpha-olefin base oil after the reaction is stable for 2-8 h; the mass ratio of the total mass of the initiator aluminum trichloride to the raw material olefin is 1:20-1: 100;
the slow release feeding mode is as follows: stage one, adding 10-20% of the total mass of the initiator at a constant speed within 30-50 minutes; stage two, 20-30% of the total mass of the initiator is added at a constant speed within 50-70 minutes; stage three, adding 20-30% of the total mass of the initiator at constant speed within 30-50 minutes; and step four, adding 30-50% of the total mass of the initiator at constant speed within 20-40 minutes.
6. The improved process for the synthesis of polyalphaolefin base oils of claim 5, wherein in step 1, the unified initiator aluminum trichloride has a particle size of one of 100 μm, 200 μm, 300 μm, and 400 μm.
7. The improved process for the synthesis of polyalphaolefin base oils of claim 5, wherein the initiator aluminum trichloride is sized uniformly by means of grinding and sieving.
8. The improved process for synthesizing polyalphaolefin base stock oil of claim 5, wherein the olefin is octene, decene, dodecene or tetradecene, the olefin is dehydrated by using molecular sieve before using, and the water content is controlled below 20 ppm.
9. An improved process for synthesizing a polyalphaolefin base oil, comprising the steps of:
step 1, unifying the particle size of the initiator aluminum trichloride to any value in 100-400 μm;
step 2, heating the raw material olefin to a target temperature of 0-10 ℃, then adding an initiator aluminum trichloride in a slow-release feeding mode, and obtaining poly-alpha-olefin base oil after the reaction is stable for 2-8 hours; the mass ratio of the total mass of the initiator aluminum trichloride to the raw material olefin is 1:20-1: 100;
the slow release feeding mode is as follows: stage one, 30-50% of the total mass of the initiator is added at a constant speed for 60-80 minutes; and in the second stage, 50-70% of the total mass of the initiator is added at constant speed for 30-50 minutes.
10. The improved process for the synthesis of polyalphaolefin base oils of claim 9, wherein in step 1, the unified initiator aluminum trichloride has a particle size of one of 100 μm, 200 μm, 300 μm, and 400 μm.
11. The improved process for the synthesis of polyalphaolefin base oils of claim 9, wherein the initiator aluminum trichloride is sized uniformly by means of grinding and sieving.
12. The improved process for the synthesis of polyalphaolefin base oils of claim 9, wherein the olefin feedstock is dehydrated by molecular sieves before use, the water content is controlled to be less than 20ppm, and the olefin is octene, decene, dodecene or tetradecene.
13. An improved process for synthesizing a polyalphaolefin base oil, comprising the steps of:
step 1, unifying the particle size of the initiator aluminum trichloride to any value in 100-400 μm;
step 2, controlling the olefin as a raw material to a target temperature of 30-50 ℃, then adding an initiator aluminum trichloride in a slow-release feeding mode, and obtaining poly-alpha-olefin base oil after the reaction is stable for 2-8 hours; the mass ratio of the total mass of the initiator aluminum trichloride to the raw material olefin is 1:20-1: 100;
the slow release feeding mode is as follows: stage one, 30-40% of the total mass of the initiator is added at a constant speed within 30-50 minutes; stage two, 30-40% of the total mass of the initiator is added at constant speed for 50-70 minutes; and in the third stage, 20-30% of the total mass of the initiator is added at constant speed within 30-50 minutes.
14. The improved process for the synthesis of polyalphaolefin base oils of claim 13, wherein in step 1, the unified initiator aluminum trichloride has a particle size of one of 100 μm, 200 μm, 300 μm, and 400 μm.
15. The improved process for the synthesis of polyalphaolefin base oils of claim 13, wherein the initiator aluminum trichloride is sized uniformly by means of grinding and sieving.
16. The improved process for the synthesis of polyalphaolefin base oils of claim 13, wherein the starting olefin is dehydrated by molecular sieve before use, the water content is controlled to be less than 20ppm, and the olefin is octene, decene, dodecene or tetradecene.
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