CN112745185A - Method for continuously producing alpha-olefin by ethylene oligomerization - Google Patents
Method for continuously producing alpha-olefin by ethylene oligomerization Download PDFInfo
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- CN112745185A CN112745185A CN201911045373.XA CN201911045373A CN112745185A CN 112745185 A CN112745185 A CN 112745185A CN 201911045373 A CN201911045373 A CN 201911045373A CN 112745185 A CN112745185 A CN 112745185A
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- 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
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a process method for continuously producing alpha-olefin by ethylene oligomerization, which separates a reaction product from a solvent and a catalyst system by an out-of-kettle flash evaporation process, returns the reaction product to a reaction kettle for ethylene oligomerization reaction under the condition that the activity of the catalyst system is kept, realizes the recycling of the catalyst and a cocatalyst, integrally reduces the adding amount of the catalyst and the cocatalyst used for producing the alpha-olefin by 50 to 80 percent, and achieves the effect of reducing the production cost of the alpha-olefin. And the by-product polymer in the ethylene oligomerization process is removed in time in the filtration process of the residual liquid after flash evaporation, so that the pipeline blockage is avoided, and the device is effectively helped to use continuous production.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, and relates to a method for continuously producing alpha-olefin by ethylene oligomerization.
Background
The preparation methods of alpha-olefin are more, and include a primary alcohol dehydration method, a Fischer-Tropsch synthesis method, an internal olefin isomerization method, an aliphatic alcohol dehydrogenation method, an extraction separation method, a paraffin cracking method, an ethylene oligomerization method and the like. Among the various preparation methods, the latter three are mainly used industrially, and ethylene oligomerization is dominant. The paraffin cracking method obtains mixed olefin with odd and even carbon numbers, the product has more impurities and poor quality, and the device using the paraffin cracking method is almost completely stopped in foreign countries by the middle of the 80 s. The ethylene oligomerization for producing the alpha-olefin is a main production route in the world at present, has the advantages of high purity, high normal ratio, good selectivity and the like of the alpha-olefin product, and can meet the requirements of downstream application, such as the alpha-olefin with high normal ratio required for being used as a polyethylene comonomer, synthesizing a polyolefin elastomer and the like.
The selective oligomerization of ethylene is one direction of the development of ethylene oligomerization. Domestic selective trimerization of ethylene has been industrialized, but selective tetramerization of ethylene is still under investigation. One of the problems which plague the industrialization thereof is the high cost of using methylaluminoxane or triisobutylaluminum-modified methylaluminoxane. Methylaluminoxane is currently totally imported and is difficult to recycle due to its solubility in solvents or alpha-olefin products. The catalyst for ethylene tetramerization usually needs more methylaluminoxane to remove impurities in a reaction system, and then is combined with the catalyst to form an active center, and the molar ratio of the methylaluminoxane to the catalyst in the ethylene tetramerization reaction is more than 300 to achieve a better catalytic effect. Another problem is that during ethylene tetramerisation, polymer formation is difficult to avoid. The polymer can be adhered to the wall of the reaction kettle during accumulation to influence heat transfer, and the continuous production is influenced by the blockage of a process pipeline.
Disclosure of Invention
The invention provides a process method for continuously producing alpha-olefin by ethylene oligomerization, which can remove polymers in a reactor by filtering in time, separate reaction products from a solvent and a catalyst system by an out-of-kettle flash evaporation process, return the reaction products to a reaction kettle for ethylene oligomerization under the condition that the activity of the catalyst system is kept, and achieve the aim of recycling the catalyst and a cocatalyst, thereby reducing the production cost.
The method adopts a method of recycling reaction bottom liquid, after the reaction is finished, the reaction liquid is conveyed into a flash tank, ethylene, optional hydrogen, reaction light components and solvent are flashed out, and the residual liquid contains active catalyst, cocatalyst, reaction product heavy components and a small amount of polymer. And (4) returning the residual liquid in the flash tank to the reaction kettle through the filter, and continuing to perform ethylene oligomerization. Thereby achieving the purposes of removing polymers and recycling active catalytic components.
The invention provides a method for continuously 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 to obtain a reaction liquid product;
s2, conveying the reaction liquid product into a flash tank for flash separation;
s3, flashing ethylene, optional hydrogen, reaction light components and solvent from the top of the tank; discharging the liquid left in the tank from the bottom of the tank; after the liquid at the bottom of the tank passes through a filter, removing the polymer, and then entering a 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 to obtain a product;
s5, conveying the reaction liquid product into a flash tank for flash separation;
s6, repeating the steps S3-S5 until the production is stopped under certain conditions, and flashing off ethylene, optional hydrogen, reaction light components and solvent from the top of the tank; discharging the liquid left in the tank from the bottom of the tank and allowing the liquid to enter a separation and recovery unit;
optionally, the light components of the product and the solvent can directly enter a separation unit, the solvent is recycled, and the light components of the reaction product are further separated.
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 operated at a pressure of 0.01 to 3.0 MPa.
According to some embodiments of the invention, the flash separation in the S2 and S5 steps is operated at a pressure of 0.02 to 2.0 MPa.
According to some embodiments of the invention, the flash separation in the S2 and S5 steps is operated at a pressure of 0.05 to 1.0 MPa.
According to some embodiments of the invention, the operating temperature of the flash separation in the S2 and S5 steps is 30-200 ℃.
According to some embodiments of the invention, the operating temperature of the flash separation in the S2 and S5 steps is 40-150 ℃.
According to some embodiments of the invention, the product is delivered into the flash tank using a pressure differential or by pump injection.
According to some embodiments of the invention, the filter is a bag filter, optionally a plurality of filters are connected in series or in parallel.
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 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 0.0001 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, 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 invention provides a process method for continuously producing alpha-olefin by ethylene oligomerization, which separates a reaction product from a solvent and a catalyst system by an out-of-kettle flash evaporation process, returns the reaction product to a reaction kettle under the condition that the activity of the catalyst system is kept, and then performs ethylene oligomerization reaction, so that the catalyst and a cocatalyst are recycled, the addition amount of the catalyst and the cocatalyst used for producing the alpha-olefin is integrally reduced by 50-80%, and the effect of reducing the production cost of the alpha-olefin is achieved. And the by-product polymer in the ethylene oligomerization process is removed in time in the filtration process of the residual liquid after flash evaporation, so that the pipeline blockage is avoided, and the device is effectively helped to use continuous production.
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.
Example 1
(1) In a 5L reactor, 1600mL of solvent toluene was added, 30mL of 10% methylaluminoxane solution in toluene was added, and 2,6-iPr described in CN105268480B was added2C6H3NHC(tBu)NPh(2-PPh2)CrCl350mg of catalyst, 5MPa of ethylene pressure, 0.05MPa of hydrogen pressure and 50 ℃ of temperature, and reacting for 3 hours.
(2) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 120 mL.
(3) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. 1480mL of toluene was supplemented. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(4) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 230 mL.
(5) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up toluene 1370 mL. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(6) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 230 mL.
(7) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up toluene 1370 mL. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(8) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 400 mL.
(9) The reaction was stopped. 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, 1600mL of toluene as a solvent was added, 30mL of a 10% methylaluminoxane solution in toluene was added, and (Ph) was added2P)2N(C2H5)CrCl360mg of catalyst, 5MPa of ethylene pressure, 0.05MPa of hydrogen pressure, 50 ℃ of temperature and 3 hours of reaction.
(2) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 120 mL.
(3) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. 1480mL of toluene was supplemented. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(4) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 230 mL.
(5) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up toluene 1370 mL. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(6) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 230 mL.
(7) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up toluene 1370 mL. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(8) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 230 mL.
(9) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up toluene 1370 mL. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours. (8) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 400 mL.
(10) The reaction was stopped. The composition of the light fraction of several reactions is shown in table 2.
TABLE 2
Example 3
(1) In a 5L reactor, 1600mL of solvent toluene was added, 30mL of 10% methylaluminoxane solution in toluene was added, and 2,6-iPr described in CN105268480B was added2C6H3NHC(tBu)NPh(2-PPh2)CrCl350mg of catalyst, 5MPa of ethylene pressure, 0.05MPa of hydrogen pressure and 50 ℃ of temperature, and reacting for 3 hours.
(2) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 120 mL.
(3) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. 1480mL of toluene was supplemented. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(4) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 230 mL.
(5) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up toluene 1370 mL. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(6) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 230 mL.
(7) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up toluene 1370 mL. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(8) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 400 mL.
(9) The reaction was stopped. The composition of the light fraction of several reactions is shown in table 3.
TABLE 3
Example 4
(1) In a 5L reactor, 1600mL of solvent toluene was added, 30mL of 10% methylaluminoxane solution in toluene was added, and 2,6-iPr described in CN105268480B was added2C6H3NHC(tBu)NPh(2-PPh2)CrCl350mg of catalyst, 5MPa of ethylene pressure, 0.05MPa of hydrogen pressure and 50 ℃ of temperature, and reacting for 3 hours.
(2) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 120 mL.
(3) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. 1480mL of toluene was supplemented. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(4) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 230 mL.
(5) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up toluene 1370 mL. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(6) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 230 mL.
(7) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up toluene 1370 mL. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(8) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 120 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 400 mL.
(9) The reaction was stopped. The composition of the light fraction of several reactions is shown in table 4.
TABLE 4
Example 5
(1) 1500mL of toluene as a solvent, 30mL of a 10% methylaluminoxane solution in toluene, and CN105268480B as a 2,6-iPr solution were placed in a 5L reactor2C6H3NHC(tBu)NPh(2-PPh2)CrCl350mg of catalyst, 5MPa of ethylene pressure, 0.05MPa of hydrogen pressure and 50 ℃ of temperature, and reacting for 3 hours.
(2) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 200 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 110 mL.
(3) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. 1380mL of toluene was added. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(4) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 200 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 130 mL.
(5) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up toluene 1370 mL. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(6) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 200 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 230 mL.
(7) The volume of the residual liquid in the flash tank is input into the reaction kettle through a filter by a pump. The temperature of the reaction kettle is 50 ℃. Make up with 1270mL of toluene. 10mL of 10% methylaluminoxane solution in toluene was supplemented, and the catalyst was 6 mg. The ethylene pressure is 5MPa, the hydrogen pressure is 0.05MPa, and the reaction is carried out for 3 hours.
(8) And conveying the liquid in the reaction kettle into a flash tank by using the pressure in the reaction kettle. Controlling the pressure of the flash tank to be 0.01MPa, simultaneously heating to 200 ℃, starting flash evaporation, and discharging the material from a flash evaporation discharge port at the top of the flash tank. And stopping flashing when the liquid level of the flash tank changes little or no along with time. Collecting the extract liquid flashed off at low temperature, and analyzing the composition of the liquid. The flash tank raffinate volume was 140 mL.
(9) The reaction was stopped. The composition of the light fraction of several reactions is shown in table 1.
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. The method for continuously producing alpha-olefin by ethylene oligomerization 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 to obtain a reaction liquid product;
s2, conveying the reaction liquid product into a flash tank for flash separation;
s3, flashing ethylene, optional hydrogen, reaction light components and solvent from the top of the tank; discharging the liquid left in the tank from the bottom of the tank; after the liquid at the bottom of the tank passes through a filter, removing the polymer, and then entering a 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 to obtain a product;
s5, conveying the reaction liquid product into a flash tank for flash separation;
s6, repeating the steps S3-S5 until the production is stopped under certain conditions, and flashing off ethylene, optional hydrogen, reaction light components and solvent from the top of the tank; discharging the liquid left in the tank from the bottom of the tank and allowing the liquid to enter a separation and recovery unit;
optionally, the light components of the product and the solvent can directly enter a separation unit, the solvent is recycled, and the light components of the reaction product are further separated.
2. The process according to claim 1, wherein the flash separation in the S2 and S5 steps is operated at a pressure of 0.01-3.0MPa, preferably 0.02-2.0MPa, more preferably 0.05-1.0 MPa;
and/or the operating temperature of the flash separation in the S2 and S5 steps is 30-200 ℃, preferably 40-150 ℃.
3. The method according to claim 1 or 2, wherein the product is conveyed into the flash tank by differential pressure or by pump injection;
and/or, the filter is a bag filter, optionally a plurality of filters are connected in series or in parallel.
4. The method of any one of claims 1 to 3, wherein the catalyst in the 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 coordination 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.
5. The method according to any one of claims 1 to 4, wherein in the step S1, the catalyst is added in an amount of 0.0005% to 0.05%, preferably 0.001% to 0.01%, more preferably 0.002% to 0.006% by mass of the solvent;
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.
6. The process according to any one of claims 1 to 5, 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.
7. The method as claimed in any one of claims 1 to 6, 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.
8. The method as claimed in any one of claims 1 to 7, 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.
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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