Solution polymerization process with improved energy utilization

专利摘要:

公开号:ES2661107T9
申请号:ES14776731.3T
申请日:2014-09-08
公开日:2018-06-21
发明作者:Terri PRICE；Fazle Sibtain；Eric Cheluget
申请人:Nova Chemicals International SA；
IPC主号:

专利说明:

5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
DESCRIPTION
Solution polymerization process with improved energy utilization Technical field
The present invention relates to an improved polymerization process in which the energy consumed is reduced and the capital cost of the polymerization plant is reduced. As the inventive solution polymerization process is producing polyethylene, energy savings are realized in the following utilities: reduced use of low pressure steam, reduced use of high pressure steam and reduced energy consumption. When the gaseous head streams of the secondary and tertiary vapor / liquid separators condense and recycle to one or more reactors upstream, energy consumption is reduced, or energy is saved, with respect to the passage of condensed head gas streams to a distillation column.
Prior art
The continuous process of polymerization in solution is well known. AND V. Kissin briefly describes, in The Kirk-Othmer Encyclopedia of Chemical Technology, in an article entitled "Polyethylene, Linear Low Density", a solution polymerization process. In the solution process, the solvent, monomer (s) and catalyst are continuously fed to a reactor. The reactor can operate in a relatively wide range of temperatures and pressures; producing a single liquid phase containing the desired polymer. Downstream from the reactor, the single liquid phase is a separate phase to recover the solvent, unreacted ethylene and a-olefins (if present) of the polymer. In the separation stage, a first vapor / liquid separator (then V / L) operating at low pressure, with respect to the reactor (s), generates: a gaseous stream of solvent head, monomers, hydrogen (in the case of be present), impurities of light end products and possibly somewhat low or fat molecular weight oligomers, and; a lower stream of a solution rich in ethylene polymer and deactivated catalyst.
The head gas stream produced in the first V / L separator is normally transported to a processing unit that separates the components into chemically distinct fractions. Several processes that achieve this separation are known; for example, a distillation column or two or more distillation columns connected in series. Such distillation operations may also include a cryogenic distillation column for ethylene separation. Distilled products, for example, solvent, comonomer (s) and ethylene can be stored in tanks or containers before being transported to the upstream solution polymerization process. Engineers skilled in the art are familiar with the design of distillation columns to achieve specific separations, for example, Perry's Chemical Engineers' Handbook (8th Edition), D.W. Green and R.H. Perry, 2008 McGraw-Hill, Section l3, "Distillation". The distillation operation is not particularly important for the success of this invention; However, this invention allows one to reduce the size and capacity of the distillation operation.
A previous Canadian application (document CA 2,809,718), related to the present invention, discloses a process in which a gaseous stream of the head of a first V / L separator is condensed and recycled to one or more reactors upstream of a high energy efficiency way; regarding the passage of this head gas stream to a distillation column.
The lower current produced in the first V / L separator can be transported to: i) a polymer recovery operation, or; ii) one or more additional V / L separators to remove additional solvent and optional comonomers. The subject matter of this application focuses on the latter, ii), as will be described in the summary of the invention below. Polymer recovery operations are not particularly important for the success of this invention. A typical polymer recovery operation includes a means for transporting the lower stream, which is a viscous stream composed essentially of molten ethylene polymer containing a small amount of deactivated catalyst and residual solvent through a devolatilization operation and, finally , through a granulator. Once granulated, and optionally dried, the ethylene polymer is generally transported to a product silo. Means for conveying the undercurrent may include gravity, gear pumps, single screw extruders, double screw extruders and subatmospheric pressure, vacuum extruders with ventilation holes that allow residual solvent or optional a-olefin comonomers to be removed.
The solution polymerization process is an intensive energy process. For example, with respect to gas phase polymerization reactors, the solution polymerization reactor (s) operate hotter, consume more steam and operate at higher pressures. There is a need to improve the energy efficiency of the continuous solution polymerization process. The present invention describes embodiments of a continuous solution polymerization process that consumes less energy, relative to a solution polymerization base case process. Since less energy is consumed, variable manufacturing costs are reduced and the environment benefits, for example, reduced greenhouse gas emissions. An added benefit of the present invention is a reduction in the amount of capital required to build a continuous plant of
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
solution polymerization.
Disclosure of the invention
The present invention provides a continuous and improved solution polymerization process in which energy consumption is reduced, comprising the following steps;
i) injecting ethylene, one or more solvents of aliphatic hydrocarbons, a catalyst, optionally, one or more olefins and optionally hydrogen in one or more upstream reactors operating at a temperature and pressure to produce an ethylene polymer in a solution single phase liquid, or, optionally, a two phase liquid solution;
ii) injecting a catalyst deactivator, downstream of one or more reactors upstream, into said single phase liquid solution, or, optionally, said two phase liquid solution, forming a deactivated reactor solution;
iii) passing said deactivated reactor solution through a heat exchanger to increase the temperature, passing said deactivated reactor solution through a pressure drop device and collecting a deactivated reactor solution in a first V separator / L forming a first lower stream of solvents rich in ethylene polymer, ethylene, deactivated catalyst and optional a-olefins and a first gaseous stream of ethylene head, solvents, oligomers, optional a-olefins and optional hydrogen;
iv) passing said first head gas stream to a distillation column, and passing said first bottom stream to a second V / L separator in which a second head gas stream and a second bottom stream are formed;
v) passing said second lower stream to a third V / L separator in which a third head gas stream and a third lower stream are formed, passing said third bottom stream, consisting essentially of molten ethylene polymer and deactivated catalyst to a polymer recovery operation;
vi) combining and condensing said second and said third head gas streams to form a recovered solvent consisting essentially of solvents, ethylene, optional a-olefins and impurities if present, and collecting said recovered solvent in a recovered solvent drum ;
vii) passing from 0% to 40% of said recovered solvent to said distillation column and passing the rest of said recovered solvent through a purification column to remove impurities, if present, forming a purified solvent ;
viii) optionally passing said purified solvent through an analytical device in which the chemical composition is determined and collecting said purified solvent in a drum of purified solvent;
ix) passing said purified solvent through a high pressure pump that forms a stream of pressurized solvent and injecting said pressurized solvent into said one or more reactors upstream.
The present invention further provides a process in which the one or more reactors operate at a temperature of 80 ° C to 300 ° C and at a pressure of 3 MPag to 45 MPag.
The present invention further provides a process in which before introducing said first V / L separator, in step iii), the temperature of said deactivated reactor solution is 150 ° C to 300 ° C and the pressure is 1 , 5 MPag to 40 MPag.
The present invention further provides a process in which said first V / L separator operates at a temperature of 100 ° C to 300 ° C and at a pressure of 1 MPag to 20 MPag.
The present invention further provides a process in which said second V / L separator operates at a temperature of 100 ° C to 300 ° C and at a pressure of 10 kPag at 1000 kPag.
The present invention further provides a process in which said third V / L separator operates at a temperature of 100 ° C to 300 ° C and at a pressure of 1 kPag to 500 kPag.
The present invention further provides a process in which said recovered solvent drum, in step vi), is at a temperature of -25 ° C to 60 ° C and a pressure of 0.1 kPag to 100 kPag.
The present invention further provides a process in which no more than 10% of said recovered solvent, formed in step vi), is passed to said distillation column and the remainder of said recovered solvent stream is passed through a purification column
The present invention further provides a process in which no more than 1% of said recovered solvent is passed through said distillation column and the remainder of said recovered solvent stream is passed through a purification column.
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
The present invention further provides a process in which said purified solvent drum, in step viii), is at a pressure of 0.1 MPag to 3 MPag.
The present invention further provides a process in which said pressurized solvent stream, formed in step ix), is at a temperature of -25 ° C to 120 ° C and a pressure of 3 MPag to 45 MPag.
The present invention further provides a process in which the solvent used in the continuous solution polymerization process is one or more C5.12 alkanes, where the alkanes can be linear or branched, or a mixture of linear and branched alkanes.
The present invention further provides a process in which said optional a-olefins are one or more C4 to Ce olefins.
The present invention further provides a process in which from 0% to 100% of said pressurized solvent stream, formed in step ix), is fed to said first reactor upstream, and the remaining pressurized solvent stream is fed to a second reactor upstream.
The present invention further provides a process in which said catalyst used to polymerize said ethylene and said optional comonomer is a heterogeneous catalyst.
The present invention further provides a process in which said catalyst used to polymerize said ethylene and said optional comonomer is a homogeneous catalyst.
The present invention further provides a process in which single or multiple reactors are used and the catalyst used in each reactor may be the same or different; Non-limiting examples of suitable catalysts include heterogeneous and homogeneous catalysts.
Phase separation in a continuous solution polymerization process may employ: i) a first V / L separator, or; ii) a first and a second V / L separator that communicate in series, or; iii) a first, a second and a third V / L separator that communicate in series, or; iv) more than three V / L separators that communicate in series. The subject matter of this application consists of a continuous solution polymerization process that uses phase separation ii), iii) or iv). More specifically, the purpose of this application is the condensation and recycling of the head gas stream produced in the second V / L separator; or the combination, condensation and recycling of gaseous head streams produced in a second and third V / L separator; or the combination, condensation and recycling of head gas streams produced in a second, third and fourth V / L separator, etc. In connection with this invention, a previous Canadian application (document CA 2,809,718) discloses a process in which the head gas stream of the first V / L separator was condensed and recycled in a manner of high energy efficiency.
DEFINITION OF TERMS
Except where otherwise indicated, all numbers that refer to process conditions (temperature, pressure, etc.), quantities of ingredients, etc., used in the specification and in the claims, are understood to be modified in all the cases by the term "approximately". Consequently, unless otherwise indicated, the numerical parameters defined in the following specification and in the appended claims are approximations that may vary significantly depending on the raw materials used or the desired ethylene polymer produced. At a minimum, and not in an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter must be interpreted at least in the light of the number of significant digits indicated and applying usual rounding techniques.
It should be understood that any numerical range cited in this document is intended to include all subintervals sub-included therein. For example, a range of "1 to 10" is intended to include all subintervals between, and including, the minimum value cited of 1 and the maximum value cited of 10; that is, it has a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. Since the numerical intervals disclosed are continuous, they can include each and every one of the values between the minimum and maximum values. Unless expressly stated otherwise, the various numerical ranges specified in this application are approximations. Similarly, a range of 0% to 100% is intended to include all subintervals between, and including, the minimum quoted value of 0% and the maximum quoted value of 100%; that is, it has a minimum value equal to or greater than 0% and a maximum value equal to less than 100%.
In order to form a more complete compression of the invention, the following terms are defined and should be used with the attached figures, the detailed description of the various embodiments and the claims.
As used herein, the term "monomer" refers to a small molecule that can chemically react and chemically bind itself or other monomers to form a polymer.
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
Non-limiting examples of monomers include ethylene (ethene), propylene (propene) and C4 to C12 a-olefins.
As used herein, the term "polymer" refers to a macromolecule composed of one or more monomers connected to each other by covalent chemical bonds. The term "polymer" means that it includes, without limitation, homopolymers (containing one type of monomer), copolymers (containing two types of monomers), terpolymers (containing three types of monomers) and four-polymers (containing four types of monomers), etc.
As used herein, the term "ethylene polymer" refers to polymers produced from the ethylene monomer and optionally one or more additional monomers. The term "ethylene polymer" means that it includes, homopolymers of ethylene, copolymers of ethylene, terpolymers of ethylene and four-polymers of ethylene, etc. Other terms commonly used to describe ethylene polymers include, but are not limited to, high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), polyethylene Ultra low density (ULDPE), plastomer and elastomers.
The term "heterogeneously branched ethylene polymer" or "heterogeneous ethylene polymer" refers to a subset of the ethylene polymer group that is produced using Ziegler-Natta or chromium catalysts.
The term "homogeneously branched ethylene polymer" or "homogeneous ethylene polymer" refers to a subset of the ethylene polymer group that is produced using a single site catalyst or metallocene catalyst. As those skilled in the art know well, the homogeneous ethylene polymer group is subsequently further subdivided into "linear homogeneous ethylene polymer" and "substantially linear homogeneous ethylene polymer". These two subgroups differ in the amount of branching of the long chain. More specifically, linear homogeneous ethylene polymers have an undetectable amount of long chain branching; while substantially linear ethylene polymers have a small amount of long chain branching, typically 0.01 long chain branching / 1000 carbons to 3 long chain / 1000 branching. A long chain branch is defined as a branch having a chain length that is macromolecular in nature, that is, the length of the long chain branch can be similar to the length of the polymer backbone to which it is attached. In this disclosure, the term "homogeneous ethylene polymer" includes both linear homogeneous ethylene polymers and substantially linear homogeneous ethylene polymers.
As used herein, the term "oligomers" refers to a low molecular weight ethylene polymer, for example, an average weighted molecular weight (Mw) ethylene polymer of about 2000 to 3000 Dalton. Other terms commonly used for oligomers include "wax" or "fat." In a solution polymerization process, the presence of oligomers in the process solvent can be problematic, for example, the oligomers can be deposited and embedded in the heat transfer surfaces.
As used herein, the term "V / L" refers to a vapor / liquid separator, in which the process stream is introduced into the V / L separator (container or tank) and separated into two streams; in which one stream is rich in ethylene polymer and the other stream is rich in solvent.
As used herein, the term "impurities of light end products" refers to chemical compounds with relatively low boiling points that may be present in the various process vessels and streams in a continuous solution polymerization process; Non-limiting examples include methane, ethane, propane, butane, nitrogen, CO2, chloroethane, HCl, etc.
As used herein, the term "oxygenated impurities" refers to traces of water, fatty acids, alcohols, ketones, aldehydes, etc .; said impurities are potential catalyst deactivating poisons.
As used herein, the term "heavy impurities" refers to linear or branched, saturated or unsaturated C8 to C30 hydrocarbons.
Brief description of the drawings
Figure 1 is a schematic view of a continuous non-inventive process of polymerization in base case solution in which the gaseous streams of head 29 and 31, produced in a second 26 and third V / L separator 28 condense and flow to a distillation column through the FL1 line.
Figure 2 is a schematic view of one embodiment of an inventive continuous solution polymerization process in which the gaseous streams of head 79 and 81 produced in the V / L separators 76 and 78 are combined and condensed; 0 to 40% of the condensed stream flows to a distillation column through the FL51 line
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
Best way to carry out the invention
An embodiment of the present invention will be described together with Figure 2. The continuous process of polymerization in comparative solution, or base case, is shown in Figure 1.
In Figure 1, solvent 1, ethylene 2 and optional a-olefin 3 are combined to produce the feed of the RF1 reactor, which is injected into the reactor 11. Several solvents are suitable; Non-limiting examples include linear or branched C5 to C12 alkanes. Non-limiting examples of a-olefins include 1-butene, 1-pentene, 1-hexene and 1-octene. The catalyst is injected into reactor 11 through line 4. The catalyst used is not specifically important for the success of this invention, suitable catalysts are described below. Optionally, hydrogen can be injected into reactor 11 through line 5; In general, hydrogen is added to finish propagating polymer chains. Hydrogen is frequently used as an agent to control the molecular weight of the ethylene polymer. Any combination of the six lines that feed the reactor 11 (lines 1 to 5 and line RF1) may or may not be heated or cooled.
The continuous solution polymerization process in Figure 1 shows a non-limiting example of two reactors, reactor 11 and reactor 12. The amount of reactors is not particularly important, provided there is at least one reactor. Recent feeds are injected into reactor 12; solvent 6, ethylene 7 and optional a-olefin 8 combine to produce the feed of the RF2 reactor. The catalyst is injected into reactor 12 through line 9. The catalyst injected into reactor 12 may be the same or different from the catalyst injected into reactor 11. Optionally, hydrogen may be injected into reactor 12 through the line 10. Any combination of the six lines that feed reactor 12 (lines 6 to 10 and line RF2) may or may not be heated or cooled.
The operating temperature of reactor 11 and 12 can range over a wide range. For example, the upper temperature limit of the reactor may be 300 ° C, in some cases 280 ° C, and in other cases 260 ° C; and the lower temperature limit of the reactor may be 80 ° C, in some cases 100 ° C, and in other cases 125 ° C. Normally, reactor 12 (the second reactor) operates at a temperature slightly higher than that of reactor 11; for example, reactor 12 is normally 5 ° C to 25 ° C warmer than reactor 11. The residence time in the reactor depends on the design and capacity of the reactor. The residence time in the reactor is normally less than 15 minutes, in some cases, less than 10 minutes and in other cases, less than 5 minutes. The operating pressure of the reactor 11 and 12 may range over a wide range. For example, the upper limit in the reactor pressure may be 45 MPag, in some cases 30 MPag, and in other cases 20 MPag; and the lower limit in the reactor pressure may be 3 MPag, in some cases 5 MPag, and in other cases 7 MPag.
Continuous solution polymerization reactors 11 and 12, shown in Figure 1, produce stream 13 containing an ethylene polymer in a single liquid phase solution, or optionally, in some operating circumstances, a two liquid phase solution . Stream 13 may also contain ethylene, active catalyst, deactivated catalyst, optional α-olefin, optional hydrogen and impurities of light end products if present.
A tank 14 contains a catalyst deactivator. Non-limiting examples of the contents of tank 14 include: (100%) net catalyst deactivator, a catalyst deactivator solution in a solvent, and; a suspension of catalyst deactivator in a liquid. Non-limiting examples of solvents and suitable liquids include linear or branched C5 to C12 alkanes. The manner in which the catalyst deactivator is added is not particularly important for the success of this invention. Once added, the catalyst deactivator substantially stops the polymerization reaction by changing the active catalyst in an inactive form. Suitable deactivators are well known in the art, non-limiting examples include: amines (for example, United States Patent No. 4,803,259 to Zboril et al.); alkali or alkaline earth metal salts of carboxylic acid (for example, United States Patent No. 4,105,609 to Machan et al.); water (for example, U.S. Patent No. 4,731,438 to Bernier et al.); hydrotalcites, alcohols and carboxylic acids (for example, United States Patent No. 4,379,882 to Miyata); or a combination thereof (U.S. Patent No. 6,180,730 to Sibtain et al.). In general, the catalyst deactivator is added in the minimum amount required to substantially deactivate the catalyst and interrupt the polymerization reaction. A minimum amount of catalyst deactivator minimizes the cost and minimizes the amount of unreacted catalyst deactivator present in the process streams.
The amount of reactors is not particularly important for the success of this invention. In addition, the shape or design of the reactors is not particularly important; for example, spherical, cylindrical or tank-type vessels that are not agitated or agitated may be used, as well as recirculating loop reactors or tubular reactors. Optionally, one or more tubular reactors may be placed after the second reactor 12 shown in Figure 1, as described in US Patent 8,101,693 issued on January 24, 2012 to Van Asseldonk et al., Assigned to NOVA Chemicals (International) SA More specifically, the current 13 in Figure 1, will flow in the tubular reactor (s) and the current that leaves the tube reactor (s) would be deactivated to form the current 15.
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
Adding the catalyst deactivator to stream 13 produces a deactivated reactor solution, stream 15. Stream 15 passes through the pressure drop device 16, the heat exchanger 17, the pressure drop device 18 , forming a deactivated reactor solution 19 of higher temperature and lower pressure that is introduced into a first V / L separator 20. Before being introduced into the first V / L separator, the deactivated reactor solution 19 may have a maximum temperature 300 ° C, in some cases 290 ° C and in other cases 280 ° C; while the minimum temperature of the deactivated reactor solution could be 150 ° C, in some cases 200 ° C and in other cases 220 ° C. Before being introduced into the first V / L separator, the deactivated reactor solution 19 may have a maximum pressure of 40 MPag, in some cases 25 MPag, and in other cases 15 MPag; while the minimum pressure could be 1.5 MPag, in some cases 5 MPag, and in other cases 6 MPag.
In the first V / L separator 20, two streams are formed: a first bottom stream 24, composed of a solvent rich in ethylene polymer, ethylene, deactivated catalyst and optional a-olefin, and; a first head gas stream 21 composed of ethylene, solvent, oligomers, optional a-olefins, optional hydrogen and impurities of light final products if present. The first V / L 20 separator can operate in a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the first V / L separator can be 300 ° C, in some cases 285 ° C, and in other cases 270 ° C; while the minimum operating temperature of the first V / L separator can be 100 ° C, in some cases 140 ° C and in other cases 170 ° C. The maximum operating pressure of the first V / L separator can be 20 MPag, in some cases 10 MPag, and in other cases 5 MPag; while the minimum operating pressure of the first V / L separator can be 1 MPag, in some cases 2 MPag, and in other cases 3 MPag.
In Figure 1, 100% of the first gaseous head stream 21 passes through the pressure control valve 22 and is sent to the distillation column through line 23.
The first lower current 24 passes through the level 25 control valve and is introduced into a second V / L separator 26. The second V / L separator can operate in a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the second V / L separator can be 300 ° C, in some cases 250 ° C, and in other cases 200 ° C; while the minimum operating temperature of the second V / L separator can be 100 ° C, in some cases 125 ° C and in other cases 150 ° C. The maximum operating pressure of the second V / L separator can be 1000 kPag, in some cases 900 kPag and in other cases 800 kPag; while the minimum operating pressure of the second V / L separator can be 10 kPag, in some cases 20 kPag and in other cases 30 kPag. As shown in Figure 1, the second V / L separator 26 produces two streams: a second bottom stream 27 comprising an ethylene polymer, solvent, ethylene, deactivated catalyst and optional a-olefins; and a second head gas stream 29 composed of solvent, optional a-olefins, ethylene and impurities if present.
The second lower current 27 flows in a third V / L separator 28. The third V / L separator can operate in a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the third V / L separator can be 300 ° C, in some cases 250 ° C, and in other cases 200 ° C; while the minimum operating temperature of the third V / L separator can be 100 ° C, in some cases 125 ° C and in other cases 150 ° C. The maximum operating pressure of the third V / L separator can be 500 kPag, in some cases 150 kPag and in other cases 100 kPag; while the minimum operating pressure of the third V / L separator can be 1 kPag, in some cases 10 kPag and in other cases 25 kPag. In the third V / L separator 28 two streams are formed: a third lower stream P1, essentially composed of a molten ethylene polymer and a deactivated catalyst, and; a third head gas stream 31 composed of solvent, optional a-olefins, ethylene and impurities if present.
The third lower current P1, shown in Figure 1, continues until polymer recovery. Non-limiting examples of polymer recovery operations include one or more gear pumps, a single spindle extruder, a double spindle extruder or a devolatilization extruder that forces molten ethylene polymer through a granulator. A devolatilization extruder can be used to remove small amounts of solvent and optional a-olefin, if present. Once granulated, the solidified ethylene polymer is optionally dried and generally transported to a product silo.
As shown in Figure 1, the second head gas stream 29, produced in the second V / L separator 26, and the third head gas stream 31, produced in the third V / L separator 28, pass through of pressure control valves 30 and 32, respectively, and combine to form stream 33. Stream 33 condenses into condenser 34 forming a condensed stream of recovered solvent 35. Recovered solvent stream is collected in a drum of recovered solvent 36. The recovered solvent drum is vented to a widening through the vent line 37. The maximum operating temperature of the recovered solvent drum can be 60 ° C, in some cases 50 ° C, and in others cases 25 ° C; while the minimum operating temperature of the recovered solvent drum can be -25 ° C, in some cases -10 ° C and in other cases 0 ° C. The maximum operating pressure of the recovered solvent drum can be 100 kPag, in some cases 50 kPag and in other cases 20 kPag; while the minimum operating pressure of the recovered solvent drum can be 0.1 kPag, in some cases 0.5 kPag and in other cases 1 kPag. Through
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
the pump inlet line 38 and the pump outlet line 40, the pump 39 pumps the recovered solvent to a distillation column through the line FL1.
An embodiment of this invention is shown in Figure 2.
In Figure 2, solvent 51, ethylene 52 and optional a-olefin 53 are combined to produce the feed of the RF51 reactor, which is injected into the reactor 61. The catalyst is injected into the reactor 61 through the line 54. Optionally, hydrogen can be injected into reactor 61 through line 55. Any combination of the six lines that feed reactor 61 (lines 51 to 55 and line RF51) may or may not be heated or cooled.
The continuous solution polymerization process in Figure 2 shows a non-limiting example of two reactors, reactor 61 and reactor 62. The amount of reactors is not particularly important for the success of this invention, provided there is less a reactor. Recent feeds are injected into reactor 62. Solvent 56, ethylene 57 and optional a-olefin 58 are combined to produce feed from reactor RF52, which is injected into reactor 62. The catalyst is injected into reactor 62. through line 59. The catalyst injected into reactor 62 may be the same or different from the catalyst injected into reactor 61. Optionally, hydrogen may be injected into reactor 62 through line 60. Any combination of the six lines that feed reactor 62 (lines 56 to 60 and line RF52) may or may not be heated or cooled.
The continuous solution polymerization reactors 61 and 62, shown in Figure 2, can operate in a relatively wide range of temperatures and pressures. For example, the upper temperature limit of the reactor may be 300 ° C, in some cases 280 ° C, and in other cases 260 ° C; and the lower temperature limit of the reactor may be 80 ° C, in some cases 100 ° C, and in other cases 125 ° C. Normally, reactor 62 (the second reactor) operates at a temperature slightly higher than that of reactor 61; for example, reactor 62 is normally 5 ° C to 25 ° C hotter than reactor 61. The residence time in the reactor is normally less than 15 minutes, in some cases, less than 10 minutes and in other cases, less At 5 minutes. The operating pressure of reactors 61 and 62 may range over a wide range. For example, the upper limit in the reactor pressure may be 45 MPag, in some cases 30 MPag, and in other cases 20 MPag; and the lower limit in the reactor pressure may be 3 MPag, in some cases 5 MPag, and in other cases 7 MPag.
Continuous solution polymerization reactors 61 and 62, shown in Figure 2, produce stream 63 containing an ethylene polymer in a single liquid phase solution, or optionally, in some operating circumstances, a two liquid phase solution . Stream 63 may also contain ethylene, active catalyst, deactivated catalyst, optional α-olefin, optional hydrogen and impurities of light end products if present.
A tank 64 contains a catalyst deactivator. Non-limiting examples of the contents of tank 64 include: (100%) net catalyst deactivator, a catalyst deactivator solution in a solvent, and; a suspension of catalyst deactivator in a liquid. Non-limiting examples of solvents and suitable liquids include linear or branched C5 to C12 alkanes. The manner in which the catalyst deactivator is added is not particularly important for the success of this invention. Once added, the catalyst deactivator substantially stops the polymerization reaction, changing the active catalyst to an inactive form. Catalyst deactivators are well known in the art, non-limiting examples include: amines; alkali metal or alkaline earth metal salts of carboxylic acids; Water; hydrotalcites; alcohols, and; carboxylic acids. In general, the catalyst deactivator is added in the minimum amount required to substantially deactivate the catalyst and interrupt the polymerization reaction. A minimum amount of catalyst deactivator minimizes the cost and minimizes the amount of unreacted catalyst deactivator present in the process streams.
The amount of reactors is not particularly important for the success of this invention. In addition, the shape or design of the reactors is not particularly important; for example, spherical, cylindrical or tank-type vessels that are not agitated or agitated may be used, as well as recirculating loop reactors or tubular reactors. A further embodiment includes the addition of one or more tubular reactors after the second reactor 62 shown in Figure 2, as described in US Patent 8,101,693, issued January 24, 2012 to Van Asseldonk et al. , assigned to NOVA Chemicals (International) SA, that is, the current 63 will flow in the tubular reactor (s) and the current that leaves the tube reactor (s) will be deactivated forming the current 65.
Adding the catalyst deactivator to stream 63 produces a deactivated reactor solution, stream 65. Stream 65 passes through the pressure drop device 66, the heat exchanger 67, the pressure drop device 68 , forming a deactivated reactor solution 69 of lower pressure and higher temperature which is introduced into a first V / L separator 70. Before being introduced into the first V / L separator, the deactivated reactor solution 69 may have a maximum temperature 300 ° C, in some cases 290 ° C and in other cases 280 ° C; while the minimum temperature of the reactor solution deactivated before entering the first V / L separator could be 150 ° C, in some cases 200 ° C and in other cases 220 ° C. Before being introduced into the first V / L separator, the deactivated reactor solution 69 may have a
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
maximum pressure of 40 MPag, in some cases 25 MPag, and in other cases 15 MPag; while the minimum pressure could be 1.5 MPag, in some cases 5 MPag, and in other cases 6 MPag.
In the first V / L 70 separator, two streams are formed: a first bottom stream 74, composed of a solvent rich in ethylene polymer, ethylene, deactivated catalyst and optional a-olefin, and; a first head gas stream 71 composed of ethylene, solvent, oligomers, optional a-olefins, optional hydrogen and impurities of light end products if present. The first V / L 70 separator can operate in a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the first V / L separator can be 300 ° C, in some cases 285 ° C, and in other cases 270 ° C; while the minimum operating temperature of the first V / L separator can be 100 ° C, in some cases 140 ° C and in other cases 170 ° C. The maximum operating pressure of the first V / L separator can be 20 MPag, in some cases 10 MPag, and in other cases 5 MPag; while the minimum operating pressure of the first V / L separator can be 1 MPag, in some cases 2 MPag, and in other cases 3 MPag.
In Figure 2, 100% of the first head gas stream 71 passes through the pressure control valve 72 and the distillation column is sent through line 73.
The first lower current 74 passes through the level 75 control valve and is introduced into a second V / L separator 76. In the second V / L separator two streams are formed: a second lower current 77 comprising a ethylene polymer, solvent, ethylene, deactivated catalyst and optional α-olefins; and a second head gas stream 79 composed essentially of solvent, ethylene, optional a-olefins, ethylene and impurities if present. The second V / L 76 separator can operate in a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the second V / L separator can be 300 ° C, in some cases 250 ° C, and in other cases 200 ° C; while the minimum operating temperature of the second V / L separator can be 100 ° C, in some cases 125 ° C and in other cases 150 ° C. The maximum operating pressure of the second V / L separator can be 1000 kPag, in some cases 900 kPag and in other cases 800 kPag; while the minimum operating pressure of the second V / L separator can be 10 kPag, in some cases 20 kPag and in other cases 30 kPag.
The second lower stream 77 flows in a third V / L separator 78. The third V / L separator can operate in a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the third V / L separator can be 300 ° C, in some cases 250 ° C, and in other cases 200 ° C; while the minimum operating temperature of the third V / L separator can be 100 ° C, in some cases 125 ° C and in other cases 150 ° C. The maximum operating pressure of the third V / L separator can be 500 kPag, in some cases 150 kPag and in other cases 100 kPag; while the minimum operating pressure of the third V / L separator can be 1 kPag, in some cases 10 kPag and in other cases 25 kPag. In the third V / L separator two currents are formed: a third lower current P2, consisting essentially of a molten ethylene polymer and a deactivated catalyst, and; a third head gas stream 81 composed of solvent, optional a-olefins, ethylene and impurities if present.
The third lower current, P2, continues until polymer recovery. Polymer recovery operations are not particularly important for the success of this invention. Non-limiting examples of polymer recovery operations include one or more gear pumps, a single spindle extruder, a double spindle extruder or a devolatilization extruder that forces molten ethylene polymer through a granulator. A devolatilization extruder can be used to remove small amounts of solvent, ethylene and optional α-olefin, if present. Once granulated, the solidified ethylene polymer is optionally dried and generally transported to a product silo.
As shown in Figure 2, the second head gas stream 79, produced in the second V / L separator 76, and the third head gas stream 81, produced in the third V / L separator 78, pass through of pressure control valves 80 and 82, respectively, and combine to form stream 83. Stream 83 condenses on condenser 84 forming a condensed stream of recovered solvent 85. Recovered solvent stream is collected in a drum of recovered solvent 86. The recovered solvent drum is vented to a widening through the vent line 87. The maximum operating temperature of the recovered solvent drum can be 60 ° C, in some cases 50 ° C, and in others cases 25 ° C; while the minimum operating temperature of the recovered solvent drum can be -25 ° C, in some cases -10 ° C and in other cases 0 ° C. The maximum operating pressure of the recovered solvent drum can be 100 kPag, in some cases 50 kPag and in other cases 20 kPag; while the minimum operating pressure of the recovered solvent drum can be 0.1 kPag, in some cases 0.5 kPag and in other cases 1 kPag.
In the inventive continuous process in solution, when the recovered solvent leaves the recovered solvent drum, a recovered solvent stream 88 is formed, which is introduced into a recovery pump 89. The output current of the recovery pump 90 is divided in two currents, FL51 and FL52, using flow controllers 91 and 92, respectively. The FL51 stream is passed to a distillation column; while the current FL52 is passed to a purification column.
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
Operationally, the solvent flow recovered through the FL52 line, see Figure 2, can vary from 100% to 0%; Given these two operating extremes, the corresponding flows through the FL51 line must be 0% and 100%, respectively. A polymerization plant is produced with an inventive lower operating cost, when the flow through the FL52 line increases. For example, in some cases more than 60% of the recovered solvent can flow through the FL52 line; in other cases more than 90% of the recovered solvent can flow through the FL52 line, and; in other additional cases more than 99% of the recovered solvent can flow through the FL52 line. When the flow of solvent recovered through the FL52 line increases, energy savings increase, reducing the operating costs of the continuous solution polymerization plant. In addition, the increase in solvent flow recovered through the FL52 line allows one to reduce the size and capacity of the distillation column, or columns, by reducing the overall capital cost of the continuous solution polymerization plant.
In some cases, a small purge flow, that is, no more than 5% of the recovered solvent flows through the FL51 line, can be advantageous if heavy impurities are introduced into the process and accumulate in the recovered solvent drum. 86. Such a purge flow allows one to remove the heaviest impurities from the continuous solution polymerization process in the distillation column. A non-limiting example of heavier impurities includes linear or branched, saturated or unsaturated C8 to C30 hydrocarbons.
With the proviso that catalyst deactivation impurities are removed in a purification step, the amount of purification beds or columns, or the arrangement of purification beds or columns (in parallel or in series) are not particularly important for The success of this invention. Non-limiting examples of deactivation impurities include oxygenated products such as: water, fatty acids, alcohols, ketones, aldehydes. A non-limiting embodiment of a purification step includes the parallel purification columns 93a and 93b, as shown in Figure 2. For example, the purification column 93a could be in line, converting the current FL52 into a current of purified solvent 94; while the purification column 93b is out of line for regeneration or replacement of the spent absorption medium if it cannot be regenerated. Similarly, purification column 93b could be in line, while purification column 93a is offline; or both purification columns 93a and 93b could be in line.
Suitable absorbent materials for removing potential catalyst deactivating poisons are well known to those skilled in the art. A non-limiting example of an absorbent suitable for removing oxygenated products is an AZ-300 absorbent bed available at UOP LLD, a Honeywell group company, 25 East Algonquin Road, Des Plaines, 1L. AZ-300 is also effective in eliminating trace levels of chloride and carbon dioxide impurities if they are present in the FL52 stream. AZ-300 is a homogeneous combination of modified activated alumina and zeolitic molecular sieve absorbers, which can be regenerated using hot gaseous nitrogen. An additional non-limiting example of suitable absorbents is a combination bed of AZ-300, at a bed inlet, and CG-731 or CG-734, at the bed outlet. CG-731 and CG-734 are available at UOP LLD, A Honeywell Group Company, 25 East Algonquin Road, Des Plaines, 1L. The absorbents CG-731 and CG-734 are effective in eliminating higher levels of carbon dioxide. CG-731 and CG-734 can be regenerated with hot gaseous nitrogen. A further non-limiting example of an absorbent suitable for removing oxygenated products is a mixed bed of Selexsorb CD and Selexsorb CDO available from BASF Corporation, Iselin, NJ, USA. Both Selexsorb CD and CDO are composed of activated alumina and can be regenerated using hot nitrogen gas.
Optionally, the purified solvent stream 94 passes through an analytical device 95 where the chemical composition of the purified solvent stream is determined. The purified solvent stream is collected in a purified solvent drum 96. Depending on the operating circumstances, the purified solvent drum 96 may have a maximum temperature of 60 ° C, in some cases 50 ° C and in other cases 25 ° C; while the minimum temperature of the purified solvent drum can be -25 ° C, in some cases -10 ° C and in other cases 0 ° C. The maximum drum pressure of the purified solvent may be 3 MPag, in some cases 2 MPag and in other cases 1 MPag; while the minimum pressure of the purified solvent drum can be 0.1 MPag, in some cases 0.2 MPag, and in other cases 0.3 MPag.
As shown in Figure 2, the solvent in the purified solvent drum 96 is passed through a high pressure pump 97, forming a pressurized solvent stream 98. The pressurized solvent stream may have a maximum temperature of 120 ° C, in some cases 80 ° C and in other cases 60 ° C; while the minimum temperature of the pressurized solvent stream can be -25 ° C, in some cases - 10 ° C, and in other cases 0 ° C. The maximum pressure of the pressurized solvent stream can be 45 MPag, in some cases 35 MPag and in other cases 25 MPag; while the minimum pressure of the pressurized solvent stream can be 3 MPag, in some cases 5 MPag, and in other cases 7 MPag.
One or more of the flow controllers are used to distribute the pressurized solvent stream 98 to one or more upstream reactors. Figure 2 shows a non-limiting example of two upstream reactors, reactor 61 and reactor 62. In Figure 2, from 0 to 100% of the pressurized solvent stream 98 passes through flow controller 99, forming a RS1 recycled solvent stream that is injected into the first reactor upstream 61; the remaining pressurized solvent stream passes through the flow controller 100, forming
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
the recycled stream RS2 that is injected into the second reactor upstream 62. One, or both, streams of recycled solvent RS1 and RS2 can be heated or cooled before being injected into the upstream reactors 61 and 62, respectively. Optionally, recycled streams RS1 and RS2 can flow controlled as desired and added to reactor feed lines RF51 and RF52, respectively, before injection into reactors 61 and 62, respectively. One or both of the RF51 and rF52 reactor feed lines may be heated or cooled before being injected into the upstream reactors 61 and 62, respectively.
A further embodiment of this invention includes a continuous solution polymerization process consisting of two vapor / liquid separators, that is, the third V / L separator 78 shown in Figure 2 is removed. This embodiment is clearly specified by the following comments and references to Figure 2: a) the third V / L separator 78 shown in Figure 2 is deleted; b) this eliminates the third head gas stream 81, and the pressure control valve 82; c) as a result, stream 83 is limited to the contents of the second head gas stream 79, and; d) the second lower stream 77, produced in the second V / L separator 76, goes directly to the polymer recovery operations. This embodiment reduces the capital cost of the solution polymerization plant, firstly through the elimination of the third V / L 78 separator, as well as reducing the size and capacity of the distillation column, or columns.
Additional embodiments of this invention also include continuous solution polymerization processes composed of more than three vapor / liquid separators (V / L). As a non-limiting example, in the case of four V / L separators, head gas streams are combined, condensed, purified and recycled from a second, a third and a fourth V / L separator to the water polymerization reactors above; while a fourth lower current, produced in the fourth V / L separator, is sent to a polymer recovery operation.
Catalysts suitable for use in the present invention are not particularly limited. The invention can be used with any metallocene or single site catalyst (SSC), Ziegler-Natta catalyst, chromium catalyst or any other organometallic catalyst capable of polymerizing olefins in a solution process. In general, the catalyst components can be premixed in the process solvent or the catalyst components can be fed as separate streams to each reactor. In some cases, premixing of the catalyst components may be desirable to provide a reaction time for the catalyst components before being introduced into the reaction. Such "in-line mixing" technique is described in several patents in the name of DuPont Canada Inc (for example, United States Patent No. 5,589,555, issued December 31, 1996).
The term "Ziegler-Natta catalyst" is well known to those skilled in the art and is used in the present invention to express its conventional meaning. Ziegler-Natta catalysts are suitable for injection through lines 4 and 9 in Figure 1, or through lines 54 and 59 in Figure 2. Ziegler-Natta catalyst systems comprise: at least one compound of transition metal in which the transition metal is selected from groups 3, 4 or 5 of the Periodic Table (using the IUPAC nomenclature), non-limiting examples include TiCU and titanium alkoxides (Ti (OR1) 4) where R1 it is a lower C1-4 alkyl radical; and an organoaluminum component, which is defined by (Al (X ') a (OR2) b (R3) c), where, X' is a halide (preferably chlorine), OR2 is an alkoxy or aryloxy group; R3 is a hydrocarbyl (preferably an alkyl having 1 to 10 carbon atoms) and, boc are each 0, 1.2 or 3 with the proviso that, a + b + c = 3 and b + c = 1 . As those skilled in the art will appreciate, conventional Ziegler Natta catalysts frequently incorporate additional components. For example, an amine or a magnesium compound or a magnesium alkyl such as butylethylmagnesium and a halide source (which is normally a chloride, for example, tertiary butyl chloride). The Ziegler-Natta catalyst may also include an electron donor, for example, an ether such as tetrahydrofuran, etc. Said components, if used, can be added to the other catalyst components before they are introduced into the reactor or they can be added directly to the reactor. The Ziegler Natta catalyst can also be "tempered" (ie, heat treated) before being introduced into the reactor (again, using techniques that are well known to those skilled in the art and published in the literature). There are a large number of techniques that describe this catalyst and the components and the sequence of addition may vary over wide ranges.
Single-site catalysts are also suitable catalysts for injection through lines 4 and 9 in Figure 1, or through lines 54 and 59 in Figure 2. The term "single site catalyst" refers to a catalyst system that produces homogeneous ethylene polymers; which may or may not contain long chain branching. There are a large number of techniques that describe single site catalyst systems, a non-limiting example includes the single site catalyst with bulky ligands of the formula:
(L) n- M- (Y) p
where M is selected from the group consisting of Ti, Zr, and Hf; L is a monoanionic ligand independently selected from the group consisting of cyclopentadienyl-type ligands, and a bulky heteroatomic ligand containing not less than five atoms in total (of which, normally, at least 20%, preferably at least 25% are numerically carbon atoms) and also contain at least one heteroatom selected from the group consisting of boron, nitrogen, oxygen, phosphorus, sulfur and silicon, said
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
bulky heteroatomic ligand binding to M with sigma or pi bonds; And it is independently selected from the group consisting of activatable ligands; n can be from 1 to 3; and p can be from 1 to 3, with the proviso that the sum of n + p is equivalent to the valence state of M, and, also, with the condition that two L-type ligands can be bridged.
Non-limiting examples of bridging groups include bridging groups containing at least one Group 13 to 16 atom, often referred to as a divalent moiety, such as, but not limited to, at least one of a carbon, oxygen, nitrogen, silicone, boron atom. , germanium and tin or a combination thereof. Preferably the bridging group contains a carbon, silicon or germanium atom, most preferably at least one silicon atom or at least one carbon atom. The bridging group may also contain substituent radicals, including halogens.
Some bridging groups include, but are not limited to, a C1-6 dialkyl radical (for example, an alkylene radical, for example, an ethylene bridge), a C6-10 diaryl radical (for example, a benzyl radical having two bond positions available), silicon or germanium radicals substituted by one or more radicals selected from the group consisting of C1-6 alkyl radical, C6-10 aryl, phosphine or amine which are unsubstituted or even completely substituted by one or more C1 alkyl radicals -6 or C6-10 aryl, or a hydrocarbyl radical such as a C1-6 alkyl or C6-10 arylene radical (eg, divalent aryl radicals); divalent C1-6 alkoxide radicals (for example, -CH2CHOHCH2-) and the like.
Examples of silyl species of bridged groups are dimethylsilyl, methylphenylsilyl, diethylsilyl, ethylphenylsilyl or diphenylsilyl compounds. The most preferred bridged species are bridged compounds of dimethylsilyl, diethylsilyl and methylphenylsilyl.
Exemplary hydrocarbyl radicals for bridged groups include methylene, ethylene, propylene, butylene, phenylene and the like, with methylene being preferred.
Exemplary bridged amides include dimethylamide, diethylamide, methylethylamide, di-t-butylamide, diisoproylamide and the like.
The term "cyclopentadienyl," often abbreviated as "Cp," refers to a 5-membered carbon ring that has a delocalized bond within the ring and normally linked to the site of the active catalyst, generally a group 4 metal (M). through links q5. The cyclopentadienyl ligand can be unsubstituted or even completely substituted with one or more substituents selected from the group consisting of C1-10 hydrocarbyl radicals in which the hydrocarbyl radicals are unsubstituted or further substituted by one or more substituents selected from the group that it consists of a halogen atom and a C1-4 alkyl radical; a halogen atom; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical; an amido radical that is unsubstituted or substituted with up to two C1-8 alkyl radicals; a phosphido radical that is unsubstituted or substituted with up to two C1-8 alkyl radicals; silyl radicals of the formula -Si- (R) 3 in which each R is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, and C6-10 aryl or aryloxy radicals; and germanyl radicals of the formula -Ge- (R) 3 in which each R is as defined above.
Typically, the cyclopentadienyl ligand is selected from the group consisting of a cyclopentadienyl radical, an indenyl radical and a fluorenyl radical where the radicals are unsubstituted or even completely substituted by one or more substituents selected from the group consisting of a fluorine atom , a chlorine atom; C1-4 alkyl radicals; and a phenyl or benzyl radical that is unsubstituted or substituted by one or more fluorine atoms.
If none of the L-type ligands is a bulky heteroatomic ligand then the catalyst could be a bis-Cp catalyst (a traditional metallocene) or a bridged restricted geometry type catalyst or tris-Cp catalyst.
If the catalyst contains one or more bulky heteroatomic ligands the catalyst would have the formula:
(D) m
(L) n - M - (Y) p
wherein M is a transition metal selected from the group consisting of Ti, Hf and Zr; D is independently a bulky heteroatom ligand (as described below); L is a monoanionic ligand selected from the group consisting of cyclopentadienyl type ligands; And it is independently selected from the group consisting of activatable ligands; m is 1 or 2; n is 0, 1 or 2; p is an integer; and the sum of m + n + p equals the valence state of M, with the proviso that when m is 2, D can be the same or different bulky heteroatomic ligands.
5
10
fifteen
twenty
25
30
35
40
Four. Five
For example, the catalyst may be a bis (phosphinimine), or a mixed complex of phosphinimine and ketimide titanium dichloride, zirconium or hafnium. Alternatively, the catalyst could contain a phosphinimine ligand or a ketimide ligand, a "L" type ligand (which is most preferably a cyclopentadienyl type ligand) and two "Y" type ligands (which are preferably both chloride).
Preferred metals (M) are from Group 4 (especially titanium, hafnium or zirconium) with titanium being the most preferred. In one embodiment, the catalysts are group 4 metal complexes in their highest oxidation state.
Bulky heteroatomic ligands (D) include, but are not limited to, phosphinimine (PI) ligands and ketimide (ketimine) ligands.
The phosphinimine ligand (PI) is defined by the formula:
R21
R21 - P = N
R21
wherein each R21 is independently selected from the group consisting of a hydrogen atom; a halogen atom; C1-20, preferably C1-10 hydrocarbyl radicals that are not substituted by or additionally substituted by a halogen atom; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical; an amido radical; a silyl radical of the formula: -Si- (R22) 3, wherein each R22 is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, and C6-10 aryl or aryloxy radicals; a germanyl radical of the formula: -Ge- (R22) 3, wherein R22 is as defined above.
Preferred phosphonimines are those in which each R21 is a hydrocarbyl radical, preferably a C1-6 hydrocarbyl radical.
Suitable phosphinimine catalysts are Group 4 organometallic complexes that contain one between a phosphinimine ligand (as described above) and an L-type ligand that is a cyclopentadienyl ligand or a heteroatomic ligand.
As used herein, the term "ketimide ligand" refers to a ligand that:
(a) is linked to the transition metal by means of a nitrogen-metal bond;
(b) has a unique substituent on the nitrogen atom (where this unique substituent is a carbon atom with double bonds to the N atom); Y
(c) has two Sub1 and Sub2 substituents (described below) that bind to the carbon atom.
Conditions a, b and c are illustrated below:
I climbed Sub2 /
C
II
N
I
metal
Where the Sub1 and Sub2 substituents can be the same or different and can be linked together additionally through a bridging group to form a ring. Example substituents include hydrocarbyls having 1 to 20 carbon atoms, preferably 3 to 6 carbon atoms, silyl groups (as described below), amido groups (as described below) and phosphide groups (as described then).
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65
For reasons of cost and convenience, it is preferred that these substituents are both hydrocarbyls, especially simple alkyls and most preferably tertiary butyl.
Ketimide catalysts are Group 4 organometallic complexes that contain a ketimide ligand (as described above) and an L-type ligand that is a cyclopentadienyl-type ligand or a heteroatomic ligand.
The term "bulky heteroatomic ligand" (D) is not limited to phosphinimine or ketimide ligands and includes ligands containing at least one heteroatom selected from the group consisting of boron, nitrogen, oxygen, phosphorus, sulfur and silicon. The heteroatomic ligand can bind to the metal with sigma or pi bonds. Exemplary heteroatomic ligands include silicon-containing heteroatomic ligands, amido ligands, alkoxy ligands, boron heterocyclic ligand and phospho ligands, as all are described below.
Heteroatomic silicon-containing ligands are defined by the formula: - (Y) SiRxRyRz in which - indicates a bond to the transition metal and Y is sulfur or oxygen. Substituents on the Si atom, in particular, Rx, Ry and Rz, are required to satisfy the binding orbital of the Si atom. The use of any particular substituent Rx, Ry or Rz is not especially important for the success of this invention. It is preferred that each of Rx, Ry and Rz be a C1-2 hydrocarbyl group (ie, methyl or ethyl) simply because said materials are rapidly synthesized from commercially available materials.
The term "amido" is intended to express its broad conventional meaning. Therefore, these ligands are characterized by (a) a nitrogen-metal bond; and (b) the presence of two substituents (which are normally simple alkyl or silyl groups) in the nitrogen atom.
The terms "alkoxy" and "aryloxy" are also intended to express their conventional meanings. Therefore, these ligands are characterized by (a) an oxygen-metal bond; and (b) the presence of a hydrocarbyl group linked to the oxygen atom. The hydrocarbyl group may be a branched or cyclic, straight chain C1-10 alkyl radical or a C6-13 aromatic radical where the radicals are unsubstituted or further substituted by one or more C1-4 alkyl radicals (eg, 2.6 diterciary butylphenoxy).
Heterocyclic boron ligands are characterized by the presence of a boron atom in a closed ring ligand. This definition includes heterocyclic ligands that also contain a ring nitrogen atom. These ligands are well known to those skilled in the art of olefin polymerization and are fully described in the literature (see, for example, U.S. Patents 5,637,659; 5,554,775; and references cited in those documents ).
The term "phosphol" is also intended to express its conventional meaning. Phospholes are cyclic dienyl structures that have four carbon atoms and a phosphorus atom in the closed ring. The simplest phosphol is C4PH4 (which is analogous to cyclopentadiene with a carbon in the ring substituted by phosphorus). Phospho ligands can be substituted with, for example, C1-20 hydrocarbyl radicals (which may optionally contain halogen substituents); phosphide radicals; amido radicals; or silyl or alkoxy radicals. Phospho ligands are well known to those skilled in the art of olefin polymerization and are described as such in U.S. Patent 5,434,116 (Sone, of Tosoh).
The present invention also contemplates the use of chromium catalysts that are well known in the art. The term "chromium catalysts" describes the olefin polymerization catalysts comprising a species of chromium, such as silyl chromate, chromium oxide or chromocene in a metal oxide support such as silica or alumina. Suitable cocatalysts for chromium catalysts are well known in the art, non-limiting examples include trialkylaluminum, alkylaluminoxane, dialkoxyalkylaluminum compounds and the like.
Example
The present invention will now be illustrated by the following non-limiting example. Computer simulations of the continuous solution polymerization processes shown in Figures 1 and 2 were performed using the Aspen Plus v7.1 and v7.2 software available on AspenTech. A second computer program, VLXE, an Excel-based thermodynamic program from VLXE, was used as a supplementary program. The Aspen Simulation Workbook program by AspenTech was used to program the exchange of data between Excel and the Aspen software.
Aspen Plus and VLXE were used to model a portion of the process from the reactor outlet, stream 13 in Figure 1 and stream 63 in Figure 2, through distillation and solvent recycling operations, but excluding polymer recovery. Many data were collected from historians of process data, sampling of process streams and measurements with field instruments to obtain the reference point in the Aspen Plus / VLXE model in order to develop a base case model in a stable state that Predict with proximity the typical process conditions for the modeled portions of the process.
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
For the base case, Figure 1, the energy consumption was calculated by adding the energy consumed by all discrete users in the form of: low pressure steam (kW), hereinafter LP vapor; high pressure steam (kW), hereinafter HP steam, and; Energy (kW) Users included all major energy consumers, for example, heat exchangers, pumps and air cooling fans, etc. The base case simulation model, Figure 1, was then modified to simulate the inventive embodiment shown in Figure 2.
With respect to the base case shown in Figure 1, the inventive embodiment shown in Figure 2 includes the following additional steps: flow controllers 91 and 92 divide the recovered solvent stream 90 into two streams FL51 and FL52, respectively; the solvent recovered in the FL52 line passes through a purification column, forming a purified solvent that is stored in a drum of purified solvent 96; The purified solvent is passed through a high pressure pump 97, forming a current of
pressurized solvent 98; the pressurized solvent passes through flow controllers 99 and 100, and is
injected into the upstream reactors 61 and 62, respectively. As a result, the recovered solvent flowing through the FL52 line borders the energy intensive distillation column (s). In contrast, in the base case, Figure 1, 100% of the recovered co-solvent is sent to a distillation column downstream through the FL1 line.
For the realization in Figure 2, the energy consumption (kW) for each utility (LP steam, HP steam and Energy) was calculated by adding the energy consumed by all users (heat exchangers, pumps and air cooling fans, etc. ) and was compared with the energy consumed in the base case of Figure 1. In the inventive embodiment, Figure 2, recycling of the solvent recovered to the upstream reactors reduced energy consumption for all users, primarily due to to the reduced solvent flow recovered from the distillation operation downstream through the FL51 line. Table 1 summarizes the energy savings associated with the embodiment shown in Figure 2 or the "Recycling Case", with respect to Figure 1 or the "Base Case".
Table 1 summarizes the flows by each route (or process line), as a percentage of the maximum possible flow. In the Base Case column of Table 1 the flow through FL1 is 100%, that is, 100% of the solvent in the recovered solvent drum 36 is sent to the distillation column. In the Recycling Case column of Table 1, the flow through FL51 is 0% and the flow through FL52 is 100%, that is, 100% of the solvent in the recovered solvent drum 86 is recycled at upstream polymerization reactors.
In the Recycling Case of Table 1 (the inventive Figure 2), the energy reductions relative to the Base Case
they are as follows: the use of LP vapor is reduced by 30%, the use of HP vapor is reduced by 44% and the use of
Energy is reduced by 13%. Energy consumption is reduced primarily due to the reduced distillation load. This example of a FL52 flow of 100%, or a 100% recycle to the upstream reactors, quantifies a maximum energy reduction, or energy savings.
Operationally, in Figure 2, the solvent flow recovered through the FL52 line can range between 100% and 0%; Given these two operating extremes, the corresponding flows through the FL51 line must be 0% and 100%, respectively. An inventive solution polymerization process is obtained with a lower operating cost when the flow through the FL52 line increases. For example, in some cases more than 60% of the recovered solvent can flow through the FL52 line; in other cases more than 90% of the recovered solvent can flow through the FL52 line, and; in other additional cases more than 99% of the recovered solvent can flow through the FL52 line. When the flow of solvent recovered through the FL52 line increases, energy savings increase, reducing the operating costs of the continuous solution polymerization plant. In addition, the increase in solvent flow recovered through the FL52 line allows one to reduce the size and capacity of the distillation column, or columns, by reducing the overall capital cost of the continuous solution polymerization plant.
In some cases, a small purge flow not exceeding 5% through the FL51 line may be advantageous if heavy impurities are introduced into the process and accumulate in the recovered solvent drum 86. Said purge flow allows one remove the heaviest impurities from the continuous solution polymerization process in the distillation column. A non-limiting example of heavy impurities includes linear or branched, saturated or unsaturated C8 to C30 hydrocarbons.
TABLE 1
 Energy simulations of the solution polymerization process; energy savings due to
 solvent recycling relative to the base case
 Figure 1: Base Case  Figure 2: Recycling Case
 Process Flow  Flow (% of maximum flow) Process Flow Flow (% of maximum flow)
 FL1 flow  100% Flow FL51 0%
 100% FL52 flow
 RS1 flow 0 to 100%
 RS2 flow 0 to 100%
 RF1 flow  100% RF51 flow <100%
 RF2 flow  100% RF52 flow <100%
 Energy savings% of Energy saved (kW) Energy savings% of Energy saved (kW)
 LP steam  0% LP Steam 30%
 HP steam  0% HP steam 44%
 Energy  0% Energy 13%
Industrial applicability
The industrial applicability of this invention is a continuous solution polymerization process that produces 5 polyethylenes in which energy consumption is reduced, capital costs are reduced and resources are conserved.
5
10
fifteen
twenty
25
30
35
40
Four. Five
fifty
55
60
65

1. A continuous and improved solution polymerization process in which energy consumption is reduced, comprising:
i) injecting ethylene, one or more aliphatic hydrocarbon solvents, a catalyst, optionally one or more olefins and optionally hydrogen, into one or more upstream reactors operating at a temperature and a pressure to produce an ethylene polymer in a single phase liquid solution, or, optionally, a two phase liquid solution;
ii) injecting a catalyst deactivator, downstream of said one or more upstream reactors, into said single phase liquid solution or, optionally, said two phase liquid solution, forming a deactivated reactor solution;
iii) passing said deactivated reactor solution through a heat exchanger to increase the temperature, passing said deactivated reactor solution through a pressure drop device and collecting said deactivated reactor solution in a first V separator / L forming a first lower stream of solvents rich in ethylene polymer, ethylene, deactivated catalyst and optional a-olefins and a first gaseous stream of ethylene head, solvent, oligomers, optional a-olefins and optional hydrogen.
iv) passing said first head gas stream to a distillation column and passing said first bottom stream to a second V / L separator in which a second head gas stream and a second bottom stream are formed; O well:
va) passing said second lower stream, consisting essentially of molten ethylene polymer and deactivated catalyst, to a polymer recovery operation and condensing said second head gas stream to form a recovered solvent consisting essentially of solvents, ethylene, α-olefins optional and impurities, if present, and collect said recovered solvent in a recovered solvent drum; or
vb-1) passing said second lower current into a third V / L separator in which a third head gas stream and a third lower stream are formed, passing said third lower stream, consisting essentially of molten ethylene polymer and catalyst deactivated, to a polymer recovery operation;
vb-2) combining and condensing said second and said third head gas streams to form a recovered solvent consisting essentially of solvents, ethylene, optional a-olefins and impurities, if present, and collecting said recovered solvent in a drum of recovered solvent;
vi) transfer from 0% to 40% of said recovered solvent to said distillation column and pass the rest of said recovered solvent through a purification column to remove impurities, if present, forming a solvent purified;
vii) optionally, passing said purified solvent through an analytical device in which the chemical composition is determined and collecting said purified solvent in a drum of purified solvent;
viii) passing said purified solvent through a high pressure pump forming a pressurized solvent stream and injecting said pressurized solvent stream into said one or more upstream reactors.
2. The process according to claim 1, wherein said one or more upstream reactors operate at a temperature of 80 ° C to 300 ° C and at a pressure of 3 MPag to 45 MPag.
3. The process according to claim 2, wherein before entering said first V / L separator, in step iii), the temperature of said deactivated reactor solution is 150 ° C to 300 ° C and the pressure of said deactivated reactor solution is 1.5 MPag to 40 MPag.
4. The process according to claim 3, wherein said first V / L separator operates at a temperature of 100 ° C to 300 ° C and at a pressure of 1 MPag to 20 MPag.
5. The process according to claim 4, wherein said second V / L separator operates at a temperature of 100 ° C to 300 ° C and at a pressure of 1 kPag at 1000 kPag.
6. The process according to claim 5, wherein said third V / L separator (if present) operates at a temperature of 100 ° C to 300 ° C and a pressure of 1 kPag to 500 kPag.
7. The process according to claim 5 or claim 6, wherein said recovered solvent drum, in step v), is at a temperature of -25 ° C to 60 ° C and a pressure of 0.1 kPag at 100 kPag
8. The process according to claim 7, wherein no more than 10% of said recovered solvent, produced in step v), is passed to said distillation column and the rest of said recovered solvent is passed to
5
10
fifteen
twenty
25
through said purification column.
9. The process according to claim 8, wherein said purified solvent drum, in step vii), operates at a temperature of -25 ° C to 60 ° C and at a pressure of 0.1 MPag to 3 MPag.
10. The process according to claim 9, wherein said pressurized solvent stream, formed in step viii), is at a temperature of -25 ° C to 120 ° C and a pressure of 3 MPag to 45 MPag.
11. The process according to claim 10, wherein said one or more aliphatic hydrocarbon solvents are C5 to C12 alkanes; wherein said hydrocarbon solvents are linear or branched hydrocarbons, or a mixture of linear and branched hydrocarbons; and wherein said optional a-olefins are one or more C4 to C8 a-olefins.
12. The process according to claim 11, wherein from 0% to 100% of said pressurized solvent stream, formed in step viii), is fed to said first reactor upstream and the remaining pressurized solvent stream is fed to a second reactor upstream.
13. The process according to claim 12, wherein said catalyst used to polymerize said ethylene and said optional α-olefins is a heterogeneous catalyst.
14. The process according to claim 12, wherein said catalyst used to polymerize said ethylene and said optional a-olefins is a homogeneous catalyst.
15. The process according to claim 12, wherein said first reactor upstream is fed a homogeneous catalyst or a heterogeneous catalyst and said second reactor upstream is fed a homogeneous catalyst or a heterogeneous catalyst.
image 1
FIGURE 1
N>
OR
51
52
53
OR
C
7J
>
ls)
image2
67
image3
98
image4
FL52

权利要求:
Claims (1)
[1]
image 1
image2

类似技术:

---

公开号 | 公开日 | 专利标题

---

ES2661107T9|2018-06-21|Solution polymerization process with improved energy utilization

---

CA2809718C|2020-03-24|Improved energy utilization in a solution polymerization plant

---

US9394383B2|2016-07-19|Monomer/diluent recovery

---

ES2364317T3|2011-08-31|POLYMERIZATION PROCEDURE IN THE MILK PHASE.

---

ES2377525T3|2012-03-28|Polymerization procedure in thick suspension phase

---

US20160289349A1|2016-10-06|System and method for polymerization

---

BR112020016056A2|2020-12-08|PROCESS

同族专利:

---

公开号 | 公开日

---

NO3055336T3|2018-05-19|

---

BR112016006015A2|2017-08-01|

---

CN106414509B|2018-05-08|

---

ES2661107T3|2018-03-27|

---

KR102192150B1|2020-12-17|

---

CA2827839A1|2015-03-19|

---

EP3055336A1|2016-08-17|

---

US20160229930A1|2016-08-11|

---

CA2827839C|2019-12-24|

---

JP2016531165A|2016-10-06|

---

WO2015040522A1|2015-03-26|

---

CN106414509A|2017-02-15|

---

US9574025B2|2017-02-21|

---

JP6419789B2|2018-11-07|

---

EP3055336B1|2017-12-20|

---

DK3055336T3|2018-02-26|

---

BR112016006015B1|2021-07-27|

---

EP3055336B9|2018-04-18|

---

KR20160058143A|2016-05-24|

---

MX2016003508A|2016-06-28|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

FR2302305B1|1975-02-28|1978-12-29|Charbonnages Ste Chimique|

---

JPS6328102B2|1980-11-12|1988-06-07|Kyowa Kagaku Kogyo Kk|

---

JPH0130848B2|1983-03-14|1989-06-22|Mitsui Toatsu Kagaku Kk|

---

GB8610126D0|1986-04-25|1986-05-29|Du Pont Canada|Isopropanolamines|

---

US4731438A|1986-12-30|1988-03-15|Union Carbide Corporation|Water treatment method for resin in a purge vessel|

---

JPH02232205A|1989-03-06|1990-09-14|Nippon Steel Chem Co Ltd|Method and apparatus for removing volatile matter|

---

JPH04142303A|1990-10-02|1992-05-15|Nippon Steel Chem Co Ltd|Removal of volatile matter|

---

US5589555A|1991-10-03|1996-12-31|Novacor Chemicals S.A.|Control of a solution process for polymerization of ethylene|

---

US5434116A|1992-06-05|1995-07-18|Tosoh Corporation|Organic transition metal compound having π-bonding heterocyclic ligand and method of polymerizing olefin by using the same|

---

US5554775A|1995-01-17|1996-09-10|Occidental Chemical Corporation|Borabenzene based olefin polymerization catalysts|

---

CA2227674C|1998-01-21|2007-04-24|Stephen John Brown|Catalyst deactivation|

---

ES2271099T3|2000-10-25|2007-04-16|Exxonmobil Chemical Patents, Inc.|PROCEDURES AND APPLIANCES FOR CONTINUOUS DISSOLUTION POLYMERIZATION.|

---

EP1630178A1|2004-08-10|2006-03-01|Innovene Manufacturing Belgium NV|Polymerisation process|

---

JP4323406B2|2004-10-04|2009-09-02|住友化学株式会社|Continuous polymerization apparatus and continuous polymerization method using the same|

---

KR100994252B1|2007-05-09|2010-11-12|주식회사 엘지화학|Ethylene alpha-olefin copolymer|

---

EP2147027B1|2007-05-16|2017-09-27|LG Chem, Ltd.|Long chain-branched ethylene-1-butene copolymer|

---

CA2598960C|2007-08-27|2015-04-07|Nova Chemicals Corporation|High temperature process for solution polymerization|

---

EP2072540A1|2007-12-20|2009-06-24|Basell Poliolefine Italia S.r.l.|Solution polymerization process for preparingpolyolefins|

---

JP5486442B2|2009-09-04|2014-05-07|出光興産株式会社|Apparatus for removing volatile components from polymerization solution, method thereof, and polymerization apparatus|

---

CA2688217C|2009-12-11|2016-07-12|Nova Chemicals Corporation|Multi reactor process|

---

CN103415560B|2011-03-08|2016-06-08|陶氏环球技术有限责任公司|Make based in the polyreaction of ethylene solvent for use circulation method and system|

---

CA2809718C|2013-03-15|2020-03-24|Nova Chemicals Corporation|Improved energy utilization in a solution polymerization plant|EP3356424B1|2015-09-29|2020-04-15|ExxonMobil Chemical Patents Inc.|Polymerization using a spiral heat exchanger|

---

CN108473601B|2015-12-21|2020-08-04|博里利斯股份公司|In-line blending process|

---

CN108602900B|2015-12-21|2021-01-05|博里利斯股份公司|Process for recovering hydrocarbons in a solution polymerization process|

---

US10047178B2|2017-02-07|2018-08-14|Exxonmobil Chemical Patents Inc.|Mitigation of catalyst inhibition in olefin polymerization|

---

CA2969280A1|2017-05-30|2018-11-30|Nova Chemicals Corporation|Non adiabatic 2-phasepolymerization process|

---

WO2019110315A1|2017-12-04|2019-06-13|Borealis Ag|A method of recovering olefins in a solution polymerisation process|

---

CN112500510A|2019-09-14|2021-03-16|南京延长反应技术研究院有限公司|Strengthening system and process for preparing polyethylene based on solution method|

---

WO2022019418A1|2020-07-22|2022-01-27|주식회사 엘지화학|Method and apparatus for recovering solvent|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

CA2827839A|CA2827839C|2013-09-19|2013-09-19|A solution polymerization process with improved energy utilization|

---

CA2827839|2013-09-19|

---

PCT/IB2014/064323|WO2015040522A1|2013-09-19|2014-09-08|A solution polymerization process with improved energy utilization|

---