CN112745179A - Method for producing alpha-olefin by ethylene oligomerization - Google Patents
Method for producing alpha-olefin by ethylene oligomerization Download PDFInfo
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- CN112745179A CN112745179A CN201911046747.XA CN201911046747A CN112745179A CN 112745179 A CN112745179 A CN 112745179A CN 201911046747 A CN201911046747 A CN 201911046747A CN 112745179 A CN112745179 A CN 112745179A
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000005977 Ethylene Substances 0.000 title claims abstract description 53
- 239000004711 α-olefin Substances 0.000 title claims abstract description 20
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 168
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 238000001704 evaporation Methods 0.000 claims abstract description 46
- 230000008020 evaporation Effects 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 121
- 239000007788 liquid Substances 0.000 claims description 89
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 238000007599 discharging Methods 0.000 claims description 26
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 8
- -1 pyridine diimine iron complex Chemical class 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000013459 approach Methods 0.000 claims description 4
- 229910000071 diazene Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 20
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 5
- 239000011636 chromium(III) chloride Substances 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Abstract
The invention discloses a process method for producing alpha-olefin by ethylene oligomerization. In the method, unreacted raw materials, most of products and solvents are separated by using the flash evaporation process of the reaction kettle, so that the catalyst and the cocatalyst are kept in the reaction kettle, the catalyst and the cocatalyst are reused, the product yield of the catalyst and the cocatalyst is improved, the addition amount of the catalyst and the cocatalyst used for producing alpha-olefin is integrally reduced, and the amount of the catalyst and the cocatalyst can be reduced by 50-80%, thereby achieving the effect of reducing the production cost of the alpha-olefin.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, and relates to a method for producing alpha-olefin by ethylene oligomerization.
Background
Alpha-olefin is an important organic raw material and an intermediate product, and carbon-carbon double bonds exist at the end position of a molecular chain, so that a series of reactions such as oxidation reaction, polymerization reaction, alkylation reaction and sulfonation reaction can be carried out. Alpha-olefins are widely used in polyethylene comonomers, surfactants, lubricants, plasticizers, polyalphaolefins, adjuvants and fine chemicals.
Compared with other processes, the method for producing alpha-olefin by ethylene oligomerization has higher purity and can meet the requirements of downstream high-end use. The ethylene oligomerization can be used for synthesizing even-numbered olefins of C4-C30 in a wide range of non-selectivity mode and also can be used for selectively synthesizing one or more alpha-olefins. The ethylene oligomerization uses metal organic compound as catalyst, such as P, O coordinated nickel catalyst, N coordinated chromium catalyst, etc. Such catalysts usually require an anhydrous and oxygen-free environment to achieve their catalytic performance, and require an aluminum alkyl or alkylaluminoxane or other co-catalyst to remove impurity components from the reaction system or to form active sites with the main catalyst. Among the ethylene oligomerization processes already in commercial use, the process of INEOS and Shell company is one in which the catalyst can be recovered. The catalyst of other processes, especially the ethylene selective oligomerization process, is a homogeneous catalyst, and is sensitive to polar substances such as water, oxygen and the like, so that the catalyst cannot be recycled. The aluminum alkyls or the alkylaluminoxanes are generally expensive, account for more production cost in the production of the alpha-olefin and even depend on import to be controlled by foreign enterprises. In the case of unrecoverable cocatalyst, increasing the utilization of alkylaluminum or alkylaluminoxane is a way to reduce the cost.
Disclosure of Invention
The invention provides a process method for producing alpha-olefin by ethylene oligomerization, which aims to improve the utilization efficiency of a catalyst and a cocatalyst in an ethylene oligomerization process, enable the catalyst and the cocatalyst which are difficult to recover to stay in a reaction kettle for a longer time, realize the repeated use of the catalyst and the cocatalyst, improve the catalyst yield and achieve the aim of reducing the production cost.
In the process, the reaction liquid is separated into extract liquid and residual liquid by a flash evaporation method in a kettle. The ethylene, the reaction light components and the solvent are separated from the reaction liquid by controlling the flash evaporation temperature, and the reaction heavy components containing the catalyst, the cocatalyst and the reaction heavy components are in the residual liquid. The residual liquid basically retains the catalyst and the cocatalyst containing activity and can be reused.
The invention provides a method for producing alpha-olefin by ethylene oligomerization, which comprises the following steps:
s1, adding a solvent, a cocatalyst, a catalyst and optional hydrogen into a reaction kettle, introducing ethylene, and carrying out ethylene oligomerization reaction to obtain a reaction solution;
s2, carrying out flash evaporation separation on the reaction liquid in the reaction kettle to obtain extract liquid and residual liquid;
s3, discharging the extract, and keeping the residual liquid in the reaction kettle;
s4, supplementing a catalyst, a cocatalyst and a solvent into the reaction kettle, introducing ethylene and optional hydrogen, and carrying out ethylene oligomerization reaction to obtain a reaction solution;
s5, carrying out flash separation on the reaction liquid to obtain an extract and a residual liquid;
s6, repeating the steps S3-S5 until certain conditions exist, stopping production, discharging the extract, and discharging the residual liquid out of the reaction kettle.
According to some embodiments of the invention, the extract and the discharged residual liquid are fed to a separation and recovery unit for separation and recovery.
The extract comprises unreacted ethylene, optional hydrogen, reaction product light components and a solvent, and the residual liquid comprises a catalyst, a cocatalyst, reaction product heavy components, a small amount of polymer, residual unreacted ethylene which is not flashed out, optional hydrogen, reaction product light components and a solvent.
According to some embodiments of the invention, the flash separation in the S2 and S5 steps is performed at an operating pressure of 0.01 to 1.0MPa and an operating temperature of 30 to 200 ℃.
According to some embodiments of the invention, the flash separation in the steps S2 and S5 is performed at an operating pressure of 0.02 to 0.5MPa and an operating temperature of 40 to 160 ℃.
According to some embodiments of the invention, the flash separation in the S2 and S5 steps is further operated at an operating pressure of 0.08 to 0.12MPa and an operating temperature of 80 to 150 ℃.
According to some embodiments of the invention, the catalyst in the S1 and S4 steps is selected from one or more of a pyridine diimine iron complex catalyst, a pyridine diimine cobalt complex catalyst, a phenanthroline iron complex catalyst, and a PNP coordinated chromium catalyst.
According to some embodiments of the present invention, the cocatalyst in the S1 and S4 steps is an aluminum-containing promoter selected from one or more of methylaluminoxane, triethylaluminum, triisobutylaluminum, and modified methylaluminoxane.
According to some embodiments of the invention, the solvent in the S1 and S4 steps is selected from one or more of toluene, cyclohexane, n-hexane, n-heptane, methylcyclohexane and xylene.
According to some embodiments of the invention, in the step S1, the solvent is added in an amount of 1 to 99% by volume of the reaction vessel.
According to some embodiments of the invention, in the step S1, the solvent is added in an amount of 10 to 80% by volume of the reaction vessel.
According to some embodiments of the invention, in the step S1, the solvent is added in an amount of 20 to 50% by volume of the reaction vessel.
According to some embodiments of the invention, in the step S1, the catalyst is added in an amount of 0.0005% to 0.05% by mass of the solvent.
According to some embodiments of the invention, the catalyst is added in an amount of 0.001% to 0.01% by mass of the solvent in the step S1.
According to some embodiments of the invention, in the step S1, the catalyst is added in an amount of 0.002% to 0.006% by mass of the solvent.
According to some embodiments of the present invention, in the step S1, the cocatalyst is added in an amount of 0.001 to 2% by mass of the solvent.
According to some embodiments of the invention, in the step S1, the cocatalyst is added in an amount of 00.01% to 1% by mass of the solvent.
According to some embodiments of the invention, in the step S1, the cocatalyst is added in an amount of 0.01% to 0.5% by mass of the solvent.
According to some embodiments of the present invention, the reaction temperature in the S1 step is 20 to 80 ℃, preferably 30 to 70 ℃, and more preferably 40 to 60 ℃.
According to some embodiments of the invention, in the step S1, the reaction ethylene partial pressure is 2.0 to 10.0 MPa.
According to some embodiments of the invention, in the step S1, the reaction ethylene partial pressure is 3.0 to 8.0 MPa.
According to some embodiments of the invention, in the step S1, the reaction ethylene partial pressure is 4.0 to 6.0 MPa.
According to some embodiments of the invention, in the step S1, the hydrogen partial pressure is 0 to 4.0 MPa.
According to some embodiments of the invention, the hydrogen partial pressure in the S1 step is 0.1 to 2.0 MPa.
According to some embodiments of the invention, in the step S1, the hydrogen partial pressure is 0.15 to 1.0 MPa.
According to some embodiments of the invention, the reaction time in the S1 step is 0.1 to 6.0 hours.
According to some embodiments of the invention, the reaction time in the S1 step is 0.2 to 4.0 hours.
According to some embodiments of the invention, the reaction time in the S1 step is 0.3 to 2.0 hours.
According to some embodiments of the invention, in the step S4, the solvent is supplemented to the reaction tank until the liquid level in the reaction tank reaches or approaches the liquid level in the step S1.
According to some embodiments of the invention, in the step S4, the catalyst and the cocatalyst are supplemented to the reaction kettle to reach or approach the content of the step S1.
According to some embodiments of the invention, the reaction temperature in the S4 step is 20 to 80 ℃.
According to some embodiments of the invention, the reaction temperature in the S4 step is 30 to 70 ℃.
According to some embodiments of the invention, the reaction temperature in the S4 step is 40-60 ℃.
According to some embodiments of the invention, in the step S4, the reaction ethylene partial pressure is 2.0 to 10.0 MPa.
According to some embodiments of the invention, in the step S4, the reaction ethylene partial pressure is 3.0 to 8.0 MPa.
According to some embodiments of the invention, in the step S4, the reaction ethylene partial pressure is 4.0 to 6.0 MPa.
According to some embodiments of the invention, in the step S4, the hydrogen partial pressure is 0.05 to 4.0 MPa.
According to some embodiments of the invention, the hydrogen partial pressure in the S4 step is 0.1 to 2.0 MPa.
According to some embodiments of the invention, in the step S4, the hydrogen partial pressure is 0.15 to 1.0 MPa.
According to some embodiments of the invention, the reaction time in the S4 step is 0.1 to 6.0 hours.
According to some embodiments of the invention, the reaction time in the S4 step is 0.2 to 4.0 hours.
According to some embodiments of the invention, the reaction time in the S4 step is 0.3 to 2.0 hours.
According to some embodiments of the invention, the certain conditions in the S6 step are that the extract has an alpha-olefin content of less than 50%.
According to some embodiments of the invention, the certain conditions in the S6 step are that the extract has an alpha-olefin content of less than 70%.
According to some embodiments of the invention, the certain conditions in the S6 step are that the extract has an alpha-olefin content of less than 80%.
According to some embodiments of the invention, the certain conditions in the S6 step are such that the volume of the raffinate does not exceed 50% of the reactor volume.
According to some embodiments of the invention, the certain conditions in the S6 step are such that the volume of the raffinate does not exceed 30% of the reactor volume.
According to some embodiments of the invention, the certain conditions in the S6 step are such that the volume of the raffinate does not exceed 20% of the reactor volume.
The invention has the beneficial effects that:
the flash evaporation process of the reaction kettle is creatively used, so that the catalyst and the cocatalyst are reused, the product yield of the catalyst and the cocatalyst is improved, the adding amount of the catalyst and the cocatalyst used for producing alpha-olefin is integrally reduced, and the amount of the catalyst and the cocatalyst can be reduced by 50-80%, thereby achieving the effect of reducing the production cost of the alpha-olefin.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic process flow diagram of one embodiment of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Methyl aluminoxane is taken as a cocatalyst, and the concentration of the toluene solution of the methyl aluminoxane is the mass-volume ratio concentration.
Example 1
(1) In a 5L reactor, 1500mL of toluene solvent were added, 35mL of 10% methylaluminoxane solution in toluene was added, and the 2,6-iPr described in CN105268480B was added2C6H3NHC(tBu)NPh(2-PPh2)CrCl360mg of catalyst, 5MPa of ethylene pressure, 0.05MPa of hydrogen pressure, 40 ℃ of temperature and 2 hours of reaction.
(2) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 150 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 105 mL.
(3) The temperature of the reaction kettle is reduced to 40 ℃. Make up with 1395mL of toluene. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, the temperature is controlled at 40 ℃, and the reaction is carried out for 1 hour.
(4) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 150 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 210 mL.
(5) The temperature of the reaction kettle is reduced to 40 ℃. Toluene 1290mL was supplemented. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, the temperature is controlled at 40 ℃, and the reaction is carried out for 1 hour.
(6) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 150 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 320 mL.
(7) The temperature of the reaction kettle is reduced to 40 ℃. Toluene 1180mL was supplemented. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, the temperature is controlled at 40 ℃, and the reaction is carried out for 1 hour.
(8) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 150 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 430 mL.
(9) The temperature of the reaction kettle is reduced to 40 ℃. Toluene was supplemented with 1070 mL. 5mL of a 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 10 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, the temperature is controlled at 40 ℃, and the reaction is carried out for 1 hour.
(10) The reaction was stopped. Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 150 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The residual liquid in the reaction kettle is discharged from the bottom. The composition of the light fraction of several reactions is shown in table 1.
TABLE 1
In table 1, "1" in "1-C6" and "1-C8" means containing one double bond. The same is as follows.
Example 2
(1) In a 5L reactor, 1500mL of toluene solvent were added, 50mL of 10% methylaluminoxane solution in toluene was added, and the 2,6-iPr described in CN105268480B was added2C6H3NHC(tBu)NPh(2-PEt2)CrCl360mg of catalyst, 4MPa of ethylene pressure, 0.1MPa of hydrogen pressure and 50 ℃ of temperature, and reacting for 3 hours.
(2) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 150 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 112 mL.
(3) The temperature of the reaction kettle is reduced to 40 ℃. Toluene was added to the reactor to make 1388 mL. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 4MPa, the hydrogen pressure is 0.1MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 1 hour.
(4) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 150 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 230 mL.
(5) The temperature of the reaction kettle is reduced to 40 ℃. Make up with 1270mL of toluene. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 4MPa, the hydrogen pressure is 0.1MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 1 hour.
(6) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 150 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 366 mL.
(7) The temperature of the reaction kettle is reduced to 40 ℃. Make up toluene 1134 mL. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 4MPa, the hydrogen pressure is 0.1MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 1 hour.
(8) The reaction was stopped. Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 150 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The residual liquid in the reaction kettle is discharged from the bottom. The composition of the light fraction of several reactions is shown in table 2.
TABLE 2
| Number of flash liquid | Activity 106g/mol Cr·h | C4(wt％) | 1-C6(wt％) | 1-C8(wt％) | Others (wt%) |
| 1 | 2.5 | 0 | 36 | 54 | 10 |
| 2 | 2.3 | 0 | 35 | 54 | 11 |
| 3 | 2.0 | 0 | 32 | 53 | 15 |
| 4 | 1.8 | 0 | 30 | 52 | 18 |
Example 3
(1) In a 5L reactor, 1500mL of toluene solvent were added, 35mL of 10% methylaluminoxane solution in toluene was added, and the 2,6-iPr described in CN105268480B was added2C6H3NHC(tBu)NPh(2-PEt2)CrCl360mg of catalyst, 4MPa of ethylene pressure, 0.1MPa of hydrogen pressure and 50 ℃ of temperature, and reacting for 3 hours.
(2) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 100 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 129 mL.
(3) The temperature of the reaction kettle was reduced to 50 ℃. Make up toluene 1371 mL. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 4MPa, the hydrogen pressure is 0.1MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 1 hour.
(4) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 100 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 390 mL.
(5) The temperature of the reaction kettle is reduced to 40 ℃. Make up with 1100mL of toluene. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 4MPa, the hydrogen pressure is 0.1MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 1 hour.
(6) The reaction was stopped. Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 150 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The residual liquid in the reaction kettle is discharged from the bottom. The composition of the light fraction of several reactions is shown in table 3.
TABLE 3
| Number of flash liquid | Activity 106g/mol Cr·h | C4(wt％) | 1-C6(wt％) | 1-C8(wt％) | Others (wt%) |
| 1 | 2.0 | 0 | 35 | 55 | 10 |
| 2 | 1.9 | 0 | 35 | 54 | 11 |
| 3 | 1.9 | 0 | 36 | 52 | 12 |
Example 4
(1) In a 5L reactor, 1500mL of solvent toluene was added, 70mL of 10% methylaluminoxane solution in toluene was added, and 2,6-iPr described in CN105268480B was added2C6H3NHC(tBu)NPh(2-PEt2)CrCl3120mg of catalyst, 5MPa of ethylene pressure, 0MPa of hydrogen pressure and 50 ℃ of temperature, and reacting for 0.5 hour.
(2) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 80 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 98 mL.
(3) The temperature of the reaction kettle was reduced to 50 ℃. The flask was supplemented with 1402mL of toluene. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 10 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 0.5 hour.
(4) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 100 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 212 mL.
(5) The temperature of the reaction kettle was reduced to 50 ℃. Make up toluene 1288 mL. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 0.5 hour.
(6) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 100 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 336 mL.
(7) The temperature of the reaction kettle was reduced to 50 ℃. 1154mL of toluene is added. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 10 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 0.5 hour.
(8) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 100 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 458 mL. The composition of the light fraction of several reactions is shown in table 4.
TABLE 4
| Number of flash liquid | Activity 106g/mol Cr·h | C4(wt％) | 1-C6(wt％) | 1-C8(wt％) | Others (wt%) |
| 1 | 2.1 | 0 | 31 | 58 | 11 |
| 2 | 2.1 | 0 | 33 | 56 | 11 |
| 3 | 2.0 | 0 | 36 | 53 | 11 |
| 4 | 1.8 | 0 | 36 | 52 | 12 |
Example 5
(1) In a 5L reactor, 1500mL of toluene solvent were added, 35mL of 10% methylaluminoxane solution in toluene was added, and the 2,6-iPr described in CN105268480B was added2C6H3NHC(tBu)NPh(2-PPh2)CrCl360mg of catalyst, 5MPa of ethylene pressure, 0.05MPa of hydrogen pressure, 50 ℃ of temperature and 2 hours of reaction.
(2) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 200 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 93 mL.
(3) The temperature of the reaction kettle was reduced to 50 ℃. Make up toluene 1407 mL. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 1 hour.
(4) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 200 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction vessel residue was 110 mL.
(5) The temperature of the reaction kettle was reduced to 50 ℃. Make up with 1390mL of toluene. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 1 hour.
(6) Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 200 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The volume of the reaction kettle raffinate was 120 mL.
(7) The temperature of the reaction kettle was reduced to 50 ℃. 1380mL of toluene was added. 5mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 5 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, the temperature is controlled at 50 ℃, and the reaction is carried out for 1 hour.
(8) The reaction was stopped. Reducing the pressure of the reaction kettle to 0.1MPa, simultaneously heating to 200 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the reaction kettle. And stopping flashing when the liquid level of the reaction kettle changes little or no along with the time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The residual liquid in the reaction kettle is discharged from the bottom. The composition of the light fraction of several reactions is shown in table 5.
TABLE 5
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A process for the production of alpha-olefins by oligomerization of ethylene comprising the steps of:
s1, adding a solvent, a cocatalyst, a catalyst and optional hydrogen into a reaction kettle, introducing ethylene, and carrying out ethylene oligomerization reaction to obtain a reaction solution;
s2, carrying out flash evaporation separation on the reaction liquid in the reaction kettle to obtain extract liquid and residual liquid;
s3, discharging the extract, and keeping the residual liquid in the reaction kettle;
s4, supplementing a catalyst, a cocatalyst and a solvent into the reaction kettle, introducing ethylene and optional hydrogen, and carrying out ethylene oligomerization reaction to obtain a reaction solution;
s5, carrying out flash separation on the reaction liquid to obtain an extract and a residual liquid;
s6, repeating the steps S3-S5 until certain conditions exist, stopping production, discharging the extract liquid, and discharging the residual liquid out of the reaction kettle;
optionally, the extract and the discharged residual liquid enter a separation and recovery unit for separation and recovery.
2. The process according to claim 1, wherein the flash separation in the S2 and S5 steps is performed at an operating pressure of 0.01-1.0MPa and an operating temperature of 30-200 ℃;
preferably, the operation pressure is 0.02-0.5MPa, and the operation temperature is 40-160 ℃;
further preferably, the operating pressure is 0.08-0.12MPa and the operating temperature is 80-150 ℃.
3. The process of claim 1 or 2, wherein the catalyst in steps S1 and S4 is selected from one or more of a pyridine diimine iron complex catalyst, a pyridine diimine cobalt complex catalyst, a phenanthroline iron complex catalyst, and a PNP coordinated chromium catalyst;
and/or the cocatalyst in the S1 and S4 steps is an aluminum-containing auxiliary agent selected from one or more of methylaluminoxane, triethylaluminum, triisobutylaluminum and modified methylaluminoxane;
and/or, the solvent in the S1 and S4 steps is selected from one or more of toluene, cyclohexane, n-hexane, n-heptane, methylcyclohexane, and xylene.
4. The method according to any one of claims 1 to 3, wherein in the step S1, the solvent is added in an amount of 1 to 99% by volume, preferably 10 to 80% by volume, and more preferably 20 to 50% by volume, based on the volume of the reaction vessel;
and/or, the adding amount of the catalyst is 0.0005 to 0.05 percent of the mass of the solvent, preferably 0.001 to 0.01 percent, and more preferably 0.002 to 0.006 percent;
and/or the addition amount of the cocatalyst is 0.001-2%, preferably 0.01-1%, and more preferably 0.01-0.5% of the mass of the solvent.
5. The process according to any one of claims 1 to 4, wherein in the step S1, the reaction temperature is 20 to 80 ℃, preferably 30 to 70 ℃, and more preferably 40 to 60 ℃;
and/or the reaction ethylene partial pressure is 2.0-10.0MPa, preferably 3.0-8.0MPa, more preferably 4.0-6.0 MPa;
and/or the hydrogen partial pressure is 0-4.0MPa, preferably 0.1-2.0MPa, more preferably 0.15-1.0 MPa;
and/or the reaction time is from 0.1 to 6.0 hours, preferably from 0.2 to 4.0 hours, more preferably from 0.3 to 2.0 hours.
6. The method as claimed in any one of claims 1 to 5, wherein in the step S4, the solvent is replenished into the reaction tank until the liquid level in the reaction tank reaches or approaches the liquid level in the step S1.
7. The method as claimed in any one of claims 1 to 6, wherein in the step S4, the catalyst and the cocatalyst are supplemented to the reaction kettle to reach or approach the content of the step S1.
8. The process according to any one of claims 1 to 9, wherein in the step S4, the reaction temperature is 20 to 80 ℃, preferably 30 to 70 ℃, more preferably 40 to 60 ℃;
and/or the reaction ethylene partial pressure is 2.0-10.0MPa, preferably 3.0-8.0MPa, more preferably 4.0-6.0 MPa;
and/or the hydrogen partial pressure is 0.05-4.0MPa, preferably 0.1-2.0MPa, more preferably 0.15-1.0 MPa;
and/or the reaction time is from 0.1 to 6.0 hours, preferably from 0.2 to 4.0 hours, more preferably from 0.3 to 2.0 hours.
9. The process according to any one of claims 1 to 8, wherein the conditions in the S6 step are such that the extract has an alpha-olefin content of less than 50%, preferably less than 70%, more preferably less than 80%.
10. The process according to any one of claims 1 to 9, wherein the conditions in the step S6 are such that the volume of the raffinate is not more than 50%, preferably not more than 30%, more preferably not more than 20% of the volume of the reactor.
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