CN110013876B - Method for continuously preparing ethylene oligomer - Google Patents
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Abstract
The invention discloses a method for continuously preparing ethylene oligomer, which comprises the steps of continuously adding reaction materials into the 1 st stage of an n-stage series reactor, sending the reaction materials into a 2 nd stage reactor after the reaction is completed, and continuously reacting until the reaction materials are conveyed to the n-stage reactor; wherein n is greater than or equal to 2; and adding mixed gas containing ethylene into the nth-stage reactor, overflowing undissolved gas from the top of the nth-stage reactor, condensing, refluxing the liquid condensate to the nth stage, introducing the gas component into the nth-1 stage, repeating the operation until the liquid condensate reflows to the 1 st stage, and introducing the gas component into an exhaust system to prepare the ethylene oligomer. The method adopts low-cost ethylene-containing mixed gas, such as enriched refinery dry gas, and adopts an iron-based main catalyst, and has the characteristics of high catalytic activity, wide oligomer distribution and multiple product types. The method has the advantages of low cost and high yield, and can comprehensively promote and utilize the dry gas of the existing refinery to generate great economic benefit.
Description
Technical Field
The invention belongs to the technical field of polyethylene preparation, and particularly relates to a method for continuously preparing an ethylene oligomer.
Background
C6The alpha-olefin is used as an important raw material in the petrochemical industry, and has wide application, wherein C is6～C10The alpha-olefins of (a) are mainly used as comonomers in Linear Low Density Polyethylene (LLDPE),the dosage is the largest, the value-added potential is the largest, and the product is the most urgent product in China at present. C12～C20The alpha-olefins of (a) are excellent intermediates for making surfactants and plasticizers. C22～C24The alpha-olefin is also used as a raw material for preparing high-grade lubricating oil. C30+ alpha-olefins, which can be used as raw material for specialty additives.
The large-scale production of higher alpha-olefins generally employs an ethylene oligomerization process, such as the worldwide well-known SHOP process, to produce C by catalyzing the ethylene oligomerization with a transition metal catalyst (referred to as SHOP catalyst)4～C30And the alpha-olefin mixture is rectified to obtain the alpha-olefin of each fraction. In 1998, the document reports that pyridine diimine Fe catalyst can produce C by catalyzing ethylene oligomerization4～C44The catalytic activity of the alpha-olefin is higher than that of a SHOP catalyst, and the selectivity of the alpha-olefin is also higher. Subsequently, the chemical institute of the Chinese academy of sciences and Chinese petroleum have worked to develop a Fe oligomerization catalyst (ZL01109134.7) having high activity and high selectivity to alpha-olefins. At present, all ethylene oligomerization methods adopt high-purity polymerization-grade ethylene raw materials, and the raw materials have high cost and are not beneficial to the popularization and industrialization of the methods.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for continuously preparing ethylene oligomer, which adopts low-cost ethylene-containing mixed gas (such as enriched refinery dry gas) as a gas raw material, thereby greatly reducing the raw material cost; in addition, the method adopts a Fe catalyst, and has the characteristics of high catalytic activity, wide oligomer distribution and multiple product types.
The purpose of the invention is realized by the following technical scheme:
a process for the continuous preparation of an ethylene oligomer, said process comprising the steps of:
(1) continuously adding an organic solvent, a cocatalyst and an iron-based main catalyst shown in formula 1 into the 1 st stage of the n-stage series reactor, allowing reaction materials to form a solution system in the reactor, and conveying the reaction materials to the 2 nd stage of the n-stage series reactor after the reaction materials stay for a certain time; repeating the steps until the reaction materials are conveyed to the nth stage of the n-stage series reactor; wherein n is greater than or equal to 2;
in the formula 1, R1-R9Identical or different, independently of one another, from H, C1-C4Alkyl of (C)1-C4Alkoxy of (a), substituted or unsubstituted phenyl; the substituent is C1-C4Alkyl, halogen, C containing halogen1-C4Alkyl groups of (a); the number of the substituent groups is 1-3;
R10-R11identical or different, independently of one another, from C1-C4Substituted or unsubstituted phenyl; the substituent is C1-C4Alkyl, halogen, C containing halogen1-C4Alkyl groups of (a); the number of the substituent groups is 1-3;
r 'and R' are identical or different and are independently selected from methyl, ethyl or n-propyl;
(2) adding mixed gas containing ethylene into the nth stage of the n-stage serial reactor, dissolving the gas into a solution system through a distribution plate, enabling undissolved gas to overflow from the top of the nth-stage serial reactor and enter a condenser, enabling a condensed liquid condensate to flow back to the nth stage of the n-stage serial reactor, and enabling a condensed gas component to enter the nth-1 stage of the n-stage serial reactor; and repeating the steps until the condensed liquid condensate flows back to the 1 st stage of the n-stage serial reactor, and the condensed gas component enters an exhaust system to prepare the ethylene oligomer.
According to the invention, the method further comprises the steps of:
(3) feeding the reaction material prepared in the nth stage of the n-stage series reactor in the step (2) into an intermediate storage tank for condensation treatment twice;
(4) and (4) feeding the reaction material subjected to condensation treatment twice in the intermediate storage tank in the step (3) into a centrifugal separation system, and performing solid-liquid phase separation to prepare the ethylene oligomer.
According to the invention, the step (1) is specifically as follows:
(1) continuously adding an organic solvent, a cocatalyst and an iron-based main catalyst shown in formula 1 into the 1 st stage of the n-stage series reactor, allowing reaction materials to form a solution system in the reactor, and conveying the materials to the 2 nd stage of the n-stage series reactor through a conveying pump after the reaction materials stay for a certain time; repeating the steps until the materials are conveyed to the nth stage of the n stages of serial reactors through the conveying pump; wherein n is 3 to 6.
According to the invention, the two times of condensation treatment in the step (3) are specifically as follows: and (3) carrying out primary condensation treatment, wherein the condensation temperature is controlled to be higher than 0 ℃, the condensed liquid condensate flows back to the intermediate storage tank, non-condensed gas is subjected to secondary condensation treatment, the condensation temperature is controlled to be lower than 0 ℃, the obtained liquid condensate after secondary condensation is separated and recovered, and other non-condensed gas enters an exhaust system.
According to the invention, the step (3) and the step (4) are specifically as follows:
(3) feeding the reaction material prepared in the nth stage of the n-stage series reactor in the step (2) into an intermediate storage tank through differential pressure, carrying out primary condensation treatment, controlling the condensation temperature to be more than 0 ℃ and less than or equal to 40 ℃, refluxing the liquid condensate after primary condensation to the intermediate storage tank, carrying out secondary condensation treatment on non-condensed gas, controlling the condensation temperature to be below 0 ℃, separating and recovering the liquid condensate (mainly comprising butylene and the like) after secondary condensation, and feeding other non-condensed gas into a discharge system;
(4) and (4) conveying the reaction material subjected to twice condensation treatment in the intermediate storage tank in the step (3) into a centrifugal separation system through a conveying pump for solid-liquid phase separation, wherein solid powder is transferred to a drying device for drying and granulation, and the liquid phase enters a separation tower for fractionation.
Preferably, in formula 1, R1-R6And R8Identical or different, independently of one another, from H, C1-C4Alkyl of (C)1-C4Alkoxy of (a), substituted or unsubstituted phenyl; the substituent is C1-C4Alkyl, halogen, C containing halogen1-C4Alkyl groups of (a); the number of the substituent groups is 1-3; r7And R9Is selected from H; r10-R11Is selected from methyl; r 'and R' are identical or different and are each independently selected from methyl, ethyl or n-propyl.
According to the present invention, the compound represented by formula 1 is selected from the group consisting of the following formula 1a, formula 1b and formula 1 c:
according to the invention, the ethylene content of the gas mixture is greater than 20 vol.%, preferably the ethylene content of the gas mixture is in the range of 50 to 99.5 vol.%; the mixed gas contains impurities which can prevent polymerization, such as CO, acetylene, alcohol, mercaptan and the like, and the content of the impurities is from ppm to ppb level, so that the activity requirement of the catalyst is met.
According to the invention, the total pressure of the ethylene-containing gas mixture is in the range of 0.1 to 10 MPa.
According to the invention, the mixed gas is the mixed gas with the ethylene content of more than 60 vol.% obtained by enriching the refinery dry gas.
According to the invention, the conversion of ethylene in the gas mixture is greater than 90%.
According to the invention, the polymerization temperature is between 60 and 100 ℃.
According to the invention, the residence time of the reaction mass in each reactor of the n series reactors is between 20 minutes and 200 minutes.
According to the invention, the cocatalyst is chosen from methylaluminoxane.
According to the invention, the molar ratio of the cocatalyst to the iron-based main catalyst shown in formula 1 is 2000:1-50: 1.
According to the invention, the organic solvent is selected from at least one of alkane organic solvents, alkene organic solvents or aromatic organic solvents, for example from at least one of n-hexane, cyclohexane, petroleum ether, toluene, xylene or hexene-1.
According to the invention, the organic solvent can also be selected from the liquid ethylene oligomerization olefin mixture prepared by the polymerization reaction.
According to the invention, the melting point of the prepared ethylene oligomer is between 40 and 125 ℃.
According to the invention, the carbon number distribution of the prepared ethylene oligomer is mainly concentrated on C4-C300In which C is4-C24The mass ratio of the components is 50-70 wt%.
The invention has the beneficial effects that:
the invention provides a method for continuously preparing ethylene oligomer, which adopts low-cost ethylene-containing mixed gas, such as enriched refinery dry gas, as a gas raw material, thereby greatly reducing the raw material cost; in addition, the method adopts an iron-based main catalyst, and has the characteristics of high catalytic activity, wide oligomer distribution and multiple product types. In a word, the method has the advantages of low cost and high yield, and can comprehensively promote and utilize the existing refinery dry gas to generate greater economic benefit.
Drawings
FIG. 1 is a process flow diagram as described in a preferred embodiment of the present invention.
In the drawing, R201 to R203 represent a stirred tank reactor in series, E201 to E203 represent condensers, C301 represents a centrifuge, D301 represents an intermediate storage tank, D302 represents a liquid mixture storage tank, and DR301 represents a dryer.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
As shown in figure 1, the process for continuously producing the ethylene oligomer by adopting the three-stage series reactor comprises the following steps:
(1) cyclohexane (250L/min), cocatalyst methylaluminoxane (10% toluene solution, 1L/min) and toluene solution (1mmol/L, 1L/min) of iron-based main catalyst shown as formula 1a are continuously added to 10m according to flow3In volume R201;
(2) continuously adding mixed gas (other components are mainly 13 wt% of ethane and 2 wt% of propane) containing 85 wt% of ethylene into an R203 reactor at a pressure of 4MPa and a flow rate of 2350Kg/h, dissolving the gas into a solution system through a distribution plate, overflowing from the top of the R203 reactor, entering a condenser E203, refluxing a liquid condensate into the R203 reactor, dissolving the gas out of the condenser E203 into a R202 reactor through the distribution plate, entering the solution system, overflowing from the top of the R202 reactor, entering a condenser E202, refluxing a liquid condensate into the R202 reactor, entering the gas out of the condenser E202 into the R201 reactor, dissolving the gas into the solution system through the distribution plate, overflowing from the top of the R201 reactor, entering the condenser E201, refluxing the liquid condensate into the R201 reactor, and entering a discharge system; the cyclization ratio of ethylene in the gas from the condenser E201 reaches 95%. The temperature of R201 to R203 is controlled between 60 and 90 ℃, and the residence time of the material flow in each reactor is 20 min.
(3) The reaction materials enter an intermediate storage tank D301 from the R203 reactor to be subjected to primary condensation treatment, the condensation temperature of the reaction materials is controlled to be more than 0 ℃ and less than or equal to 40 ℃, the liquid condensate after the primary condensation flows back to the intermediate storage tank, the non-condensed gas is subjected to secondary condensation treatment, the condensation temperature of the non-condensed gas is controlled to be below 0 ℃, the liquid condensate after the secondary condensation is subjected to butylene separation and recovery, and other non-condensed gas enters an exhaust system;
(4) the material in the middle storage tank D301 enters a centrifugal separation system C301 through a delivery pump, solid and liquid phases in the mixed material are separated, solid powder is transferred to a drying device DR301, the dried mixed material is granulated, and the liquid phase enters a storage tank D302 and is delivered to a separation tower from the D302 for fractionation.
The results of the ethylene oligomer analysis were as follows: c4-C2470.5 wt% of the total amount of the oligomers, C24+Accounting for 29.5 wt% of the total oligomer, and the melting range of the prepared ethylene oligomer is between 40 and 123 ℃.
Example 2
As shown in figure 1, the process for continuously producing the ethylene oligomer by adopting the three-stage series reactor comprises the following steps:
(1) the C prepared in example 14-C24The mixed solution (250L/min), the cocatalyst methylaluminoxane (10% toluene solution, 1L/min) and the toluene solution (1mmol/L, 1L/min) of the iron-based main catalyst shown as the formula 1b are continuously added to 10m according to the flow3In volume R201;
(2) continuously adding mixed gas (other components are mainly 13 wt% of ethane and 2 wt% of propane) containing 70 wt% of ethylene into an R203 reactor at a pressure of 4MPa and a flow rate of 2850Kg/h, dissolving the gas into a solution system through a distribution plate, overflowing from the top of the R203 reactor, entering a condenser E203, refluxing a liquid condensate into the R203 reactor, dissolving the gas out of the condenser E203 into a R202 reactor through the distribution plate, entering the solution system, overflowing from the top of the R202 reactor, entering a condenser E202, refluxing a liquid condensate into the R202 reactor, entering the gas out of the condenser E202 into the R201 reactor, dissolving the gas into the solution system through the distribution plate, overflowing from the top of the R201 reactor, entering the condenser E201, refluxing the liquid condensate into the R201 reactor, and entering a discharge system; the cyclization ratio of ethylene in the gas from the condenser E201 reaches 97%. The temperature of R201 to R203 is controlled between 60 and 90 ℃, and the residence time of the material flow in each reactor is 20 min.
(3) The reaction materials enter an intermediate storage tank D301 from the R203 reactor to be subjected to primary condensation treatment, the condensation temperature of the reaction materials is controlled to be more than 0 ℃ and less than or equal to 40 ℃, the liquid condensate after the primary condensation flows back to the intermediate storage tank, the non-condensed gas is subjected to secondary condensation treatment, the condensation temperature of the non-condensed gas is controlled to be below 0 ℃, the liquid condensate after the secondary condensation is subjected to butylene separation and recovery, and other non-condensed gas enters an exhaust system;
(4) the material in the middle storage tank D301 enters a centrifugal separation system C301 through a delivery pump, solid and liquid phases in the mixed material are separated, solid powder is transferred to a drying device DR301, the dried mixed material is granulated, and the liquid phase enters a storage tank D302 and is delivered to a separation tower from the D302 for fractionation.
The results of the ethylene oligomer analysis were as follows: c4-C24Based on 62 wt% of the total amount of the oligomers, C24+Accounting for 38 wt% of the total oligomer, and the melting range of the prepared ethylene oligomer is 40-123 ℃.
Example 3
As shown in figure 1, the process for continuously producing the ethylene oligomer by adopting the three-stage series reactor comprises the following steps:
(1) the C prepared in example 14-C24The mixed solution (250L/min), the cocatalyst methylaluminoxane (10% toluene solution, 1L/min) and the toluene solution (1mmol/L, 1L/min) of the iron-based main catalyst shown as the formula 1c are continuously added to 10m according to the flow3In volume R201;
(2) continuously adding mixed gas (other components are mainly 13 wt% of ethane and 2 wt% of propane) containing 60 wt% of ethylene into an R203 reactor at a pressure of 4MPa and a flow rate of 3150Kg/h, dissolving the gas into a solution system through a distribution plate, overflowing from the top of the R203 reactor, entering a condenser E203, refluxing a liquid condensate into the R203 reactor, dissolving the gas out of the condenser E203 into a R202 reactor through the distribution plate, entering the solution system, overflowing from the top of the R202 reactor, entering a condenser E202, refluxing a liquid condensate into the R202 reactor, entering the gas out of the condenser E202 into the R201 reactor, dissolving the gas into the solution system through the distribution plate, overflowing from the top of the R201 reactor, entering the condenser E201, refluxing the liquid condensate into the R201 reactor, and entering a discharge system; the cyclization ratio of ethylene in the gas from the condenser E201 reaches 98%. The temperature of R201 to R203 is controlled between 60 and 90 ℃, and the residence time of the material flow in each reactor is 20 min.
(3) The reaction materials enter an intermediate storage tank D301 from the R203 reactor to be subjected to primary condensation treatment, the condensation temperature of the reaction materials is controlled to be more than 0 ℃ and less than or equal to 40 ℃, the liquid condensate after the primary condensation flows back to the intermediate storage tank, the non-condensed gas is subjected to secondary condensation treatment, the condensation temperature of the non-condensed gas is controlled to be below 0 ℃, the liquid condensate after the secondary condensation is subjected to butylene separation and recovery, and other non-condensed gas enters an exhaust system;
(4) the material in the middle storage tank D301 enters a centrifugal separation system C301 through a delivery pump, solid and liquid phases in the mixed material are separated, solid powder is transferred to a drying device DR301, the dried mixed material is granulated, and the liquid phase enters a storage tank D302 and is delivered to a separation tower from the D302 for fractionation.
The results of the ethylene oligomer analysis were as follows: c4-C24Based on the total amount of the oligomers (53 wt.%), C24+Accounting for 47 wt% of the total oligomer, and the melting range of the prepared ethylene oligomer is 40-123 ℃.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. A process for the continuous preparation of an ethylene oligomer, characterized in that it comprises the following steps:
(1) continuously adding an organic solvent, a cocatalyst and an iron-based main catalyst shown in formula 1 into the 1 st stage of the n-stage series reactor, allowing reaction materials to form a solution system in the reactor, and conveying the reaction materials to the 2 nd stage of the n-stage series reactor after the reaction materials stay for a certain time; repeating the steps until the reaction materials are conveyed to the nth stage of the n-stage series reactor; wherein n is greater than or equal to 2;
in the formula 1, R1-R9Identical or different, independently of one another, from H, C1-C4Alkyl of (C)1-C4Alkoxy of (a), substituted or unsubstituted phenyl; the substituent is C1-C4Alkyl, halogen, C containing halogen1-C4Alkyl groups of (a); the number of the substituent groups is 1-3;
R10-R11identical or different, independently of one another, from C1-C4Substituted or unsubstituted phenyl; the substituent is C1-C4Alkyl, halogen, C containing halogen1-C4Alkyl groups of (a); the number of the substituent groups is 1-3;
r 'and R' are identical or different and are independently selected from methyl, ethyl or n-propyl;
(2) adding mixed gas containing ethylene into the nth stage of the n-stage serial reactor, dissolving the gas into a solution system through a distribution plate, enabling undissolved gas to overflow from the top of the nth-stage serial reactor and enter a condenser, enabling a condensed liquid condensate to flow back to the nth stage of the n-stage serial reactor, and enabling a condensed gas component to enter the nth-1 stage of the n-stage serial reactor; repeating the steps until the condensed liquid condensate flows back to the 1 st stage of the n-stage serial reactor, and the condensed gas component enters an exhaust system to prepare the ethylene oligomer; the mixed gas is obtained by enriching refinery dry gas, the content of ethylene is more than 60 vol%, the mixed gas contains impurities which can hinder polymerization, such as CO, acetylene, alcohol and mercaptan, and the content of the impurities is from ppm to ppb level, so that the activity requirement of the catalyst is met;
(3) feeding the reaction material prepared in the nth stage of the n-stage series reactor in the step (2) into an intermediate storage tank for condensation treatment twice;
(4) feeding the reaction material subjected to condensation treatment twice in the intermediate storage tank in the step (3) into a centrifugal separation system, and performing solid-liquid phase separation to prepare an ethylene oligomer; the melting point of the ethylene oligomer is between 40 and 125 ℃, and the carbon number distribution of the ethylene oligomer is mainly concentrated on C4-C300In which C is4-C24The mass ratio of the components is 50-70 wt%.
2. The method according to claim 1, characterized in that step (1) is in particular:
(1) continuously adding an organic solvent, a cocatalyst and an iron-based main catalyst shown in formula 1 into the 1 st stage of the n-stage series reactor, allowing reaction materials to form a solution system in the reactor, and conveying the materials to the 2 nd stage of the n-stage series reactor through a conveying pump after the reaction materials stay for a certain time; repeating the steps until the materials are conveyed to the nth stage of the n stages of serial reactors through the conveying pump; wherein n is 3 to 6.
3. The method according to claim 1, wherein the two condensation treatments of step (3) are in particular: and (3) carrying out primary condensation treatment, wherein the condensation temperature is controlled to be higher than 0 ℃, the condensed liquid condensate flows back to the intermediate storage tank, non-condensed gas is subjected to secondary condensation treatment, the condensation temperature is controlled to be lower than 0 ℃, the obtained liquid condensate after secondary condensation is separated and recovered, and other non-condensed gas enters an exhaust system.
4. The method according to claim 1, characterized in that the steps (3) and (4) are in particular:
(3) feeding the reaction material prepared in the nth stage of the n-stage series reactor in the step (2) into an intermediate storage tank through differential pressure, carrying out primary condensation treatment, controlling the condensation temperature to be more than 0 ℃ and less than or equal to 40 ℃, refluxing the liquid condensate after primary condensation to the intermediate storage tank, carrying out secondary condensation treatment on non-condensed gas, controlling the condensation temperature to be below 0 ℃, separating and recovering butene from the liquid condensate after secondary condensation, and feeding other non-condensed gas into a discharge system;
(4) and (4) conveying the reaction material subjected to twice condensation treatment in the intermediate storage tank in the step (3) into a centrifugal separation system through a conveying pump for solid-liquid phase separation, wherein solid powder is transferred to a drying device for drying and granulation, and the liquid phase enters a separation tower for fractionation.
5. The method according to claim 1, wherein R in formula 11-R6And R8Identical or different, independently of one another, from H, C1-C4Alkyl of (C)1-C4Alkoxy of (a), substituted or unsubstituted phenyl; the substituent is C1-C4Alkyl, halogen, C containing halogen1-C4Alkyl groups of (a); the number of the substituent groups is 1-3; r7And R9Is selected from H; r10-R11Is selected from methyl; r 'and R' are identical or different and are each independently selected from methyl, ethyl or n-propyl.
6. The method according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of formula 1a, formula 1b, and formula 1c below:
7. the method of claim 1, wherein the ethylene content of the mixed gas is in the range of 60 to 99.5 vol.%.
8. The method according to claim 1, wherein the total pressure of the ethylene-containing gas mixture is in the range of 0.1 to 10 MPa.
9. The method of claim 1, wherein the conversion of ethylene in the mixed gas is greater than 90%.
10. The process according to claim 1, wherein the polymerization temperature is 60-100 ℃.
11. The process of claim 1, wherein the residence time of the reaction mass in each reactor of the n series reactors is in the range of 20 minutes to 200 minutes.
12. The process of claim 1, wherein the cocatalyst is selected from methylaluminoxane;
and/or the molar ratio of the cocatalyst to the iron-based main catalyst shown in the formula 1 is 2000:1-50: 1.
13. The method according to claim 1, wherein the organic solvent is selected from at least one of n-hexane, cyclohexane, petroleum ether, toluene, xylene, or hexene-1;
or the organic solvent is selected from the liquid ethylene oligomerization olefin mixture prepared by the polymerization reaction.
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| US20100249480A1 (en) * | 2009-03-31 | 2010-09-30 | Nicholas Christopher P | Process for Oligomerizing Dilute Ethylene |
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| CN105732849A (en) * | 2014-12-09 | 2016-07-06 | 中国石油化工股份有限公司 | Olefin polymerization device and method |
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| CN101671405A (en) * | 2008-09-08 | 2010-03-17 | 住友化学株式会社 | Apparatus and method for producing polyolefin |
| US20100249480A1 (en) * | 2009-03-31 | 2010-09-30 | Nicholas Christopher P | Process for Oligomerizing Dilute Ethylene |
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