systems and methods for recovering hydrocarbons from a gaseous product from the polyolefin purge

专利摘要:
SYSTEM AND METHOD FOR RECOVERING HYDROCARBONS FROM A GASEOUS PRODUCT FROM POLYOLEFINE PURGE. The present invention relates to the system and methods for separating a purified gas recovered from a polyethylene product. The method may include recovering a polyethylene product containing one or more volatile hydrocarbons from a polymerization reactor and contacting the polyethylene product with a purge gas to remove at least a portion of the volatile hydrocarbons to produce a polymeric product having a concentration reduced amount of volatile hydrocarbons and a gaseous purge product enriched in volatile hydrocarbons. The gaseous purging product can be compressed at a pressure of approximately 2,500 kPaa to approximately 10,000 kPaa, and then can be cooled and separated into at least a first product, a second product and a third product. A portion of one or more of the first, second or third products can then be recycled as a purge gas, in the polymerization reactor, or in the purge gas product enriched in volatile hydrocarbons prior to compression, respectively.
公开号:BR112013014992B1
申请号:R112013014992-2
申请日:2011-12-13
公开日:2020-12-29
发明作者:Mark W. Blood；Randall L. Force；Theodore D. Duncan；George W. Schwarz Jr.；Daniel W. Mosser；Donald A. Fischer；Robert D. Olson；James L. Swecker；Cloid Russell Smith
申请人:Univation Technologies, Llc；
IPC主号:

专利说明:

BACKGROUND
[0001] In gas phase polymerization, a gas stream containing one or more monomers is passed through a fluidized bed under reactive conditions in the presence of a catalyst. A polymeric product is removed from the reactor while the fresh monomer is introduced into the reactor. Gaseous components and / or residual liquids such as unreacted hydrocarbon monomer (s) and / or diluent (s) are normally absorbed into the polymeric product. These volatile, unreacted monomers and / or diluents have to be removed from the polymerized particles.
[0002] Typically, the polymeric product is introduced into a product separator or purge compartment and contacted with a counter-current flow of a purge gas such as nitrogen. The recovered purge gas product, which includes purge gas and unreacted volatile monomers and / or diluents, is burned, used as a fuel or undergoes further processing to recover the valuable monomers and / or diluents. Current separation systems use separation of membrane, adsorbent materials and / or adsorption with pressure oscillation. Although some valuable monomers and / or diluents are recovered, the remaining nitrogen purge gas must be burned or consumed as a fuel because the concentration of monomers and / or diluents in the purge gas remains too high.
[0003] There is a need, therefore, for improved systems and methods for recovering hydrocarbons from a polymerization purge gas. SUMMARY
[0004] Systems and methods for recovering hydrocarbons from the gaseous product of purging a polyolefin are provided. The method may include recovering a polyolefin product comprising one or more volatile hydrocarbons from a polymerization reactor and contacting the polyolefin product with a purge gas to remove at least a portion of the volatile hydrocarbons to produce a polyolefin product having a reduced concentration of volatile hydrocarbons and a gaseous purge product enriched in volatile hydrocarbons. Volatile hydrocarbons can include hydrogen, methane, one or more C2-C12 hydrocarbons or any combination thereof. The gaseous product of the purge can be at a pressure of approximately 50 kPa to approximately 250 kPa. The method may also include compressing the gaseous product from the purge at a pressure of approximately 2,500 kPa to approximately 10,000 kPa. The method can also include cooling and separating the gaseous product from the compressed purge into at least one first product, a second product and a third product. The method may also include recycling at least a portion of at least one first product as a purge gas, the second product for the polymerization reactor and the third product for the purge gas product enriched in volatile hydrocarbons prior to compression.
[0005] The system for recovering hydrocarbons from the gaseous product of a polyolefin purge may include a purge compartment, a compression system, a cooling system, and at least one recycle line. The purge compartment can be adapted to receive a polyolefin product comprising one or more volatile hydrocarbons from a polymerization reactor. The polyolefin product can be contacted with a purge gas inside the purge compartment to remove at least a portion of the volatile hydrocarbons to produce a polyolefin product having a reduced concentration of volatile hydrocarbons and a gaseous purge product enriched in volatile hydrocarbons. Volatile hydrocarbons can include hydrogen, methane, one or more C2-C12 hydrocarbons or any combination thereof. The gaseous product of the purge can be at a pressure of approximately 50 kPa to approximately 250 kPa. The compression system can be adapted to compress the gaseous product from the purge to a pressure of approximately 2,500 kPa to approximately 10,000 kPa. The cooling system can be adapted to cool and separate the gaseous product from the compressed purge into at least one first product, a second product and a third product. At least one recycle line can be adapted to recycle at least a portion of at least one first product such as purge gas, the second product for the polymerization reactor and the third product for the gaseous purging product enriched in volatile hydrocarbons before compression.
[0006] In the method and system described in this application, the polyolefin product may comprise polyethylene homopolymers, polypropylene homopolymers, polyethylene copolymers or polypropylene copolymers.
[0007] In the method and system described in this application, the cooling system can be a self-cooling system. BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Figure 1 represents a schematic diagram of an illustrative polymerization system for producing polymer products and recovering volatiles from it.
[0009] Figure 2 represents a schematic diagram of an illustrative compression system for compressing a gaseous purged product recovered from a polymerization system.
[0010] Figure 3 represents a schematic diagram of an illustrative compression system for compressing a gaseous purged product recovered from a polymerization system.
[0011] Figure 4 represents a schematic diagram of an illustrative polymerization system for producing one or more polymer products and recovering volatiles from it.
[0012] Figure 5 represents a schematic diagram of an illustrative gas phase polymerization system. DETAILED DESCRIPTION
[0013] Figure 1 represents a schematic diagram of an illustrative polymerization system 100 for producing one or more polymer products and recovering volatiles from it. A reactor feed through line 101 and a catalyst feed through line 102 can be introduced into a polymerization reactor 103 where the reactor feed can be polymerized to produce a polymeric product. The polymeric product through line 104 can be recovered from polymerization reactor 103 and introduced into one or more product discharge systems 105. Within product discharge system 105, a first portion of any volatile contained in the polymeric product through line 106 can be recovered from it and recycled to reactor 103. An auxiliary product discharge gas via line 107 can be introduced into the product discharge system 105 and the polymeric product via line 108 can be transferred from product discharge system 105 for one or more purge compartments 115. Auxiliary product discharge gas through line 107 can facilitate the transfer or transport of the polymeric product through line 108 of product discharge system 105 to purge compartment 115. One or more devices flow control valves, for example, 109, 110, and 111 valves, can be used to control the introduction of the polymeric product through the line 104 in product discharge system 105, removal of the first portion of volatiles through line 106 and removal of polymeric product through line 108, respectively, from product discharge system 105. The particular timing sequence of the control devices flow rates 109, 110, 111 can be accomplished by using conventional programmable controllers that are known in the art.
[0014] A purge gas through line 112 can be introduced into the purge compartment 115 and can contact the polymeric product within the purge compartment 115 to separate at least a portion of any remaining volatile polymeric product. The purge gas and the separate volatiles or "gaseous purge product" via line 116 and the polymeric product via line 117 can be recovered from the purge compartment 115. The polymeric product via line 117 can be introduced into a storage, packaged and shipped as a final product, further processed into one or more products, for example, processed into a film or other article and / or mixed with one or more polymers, etc., or any combination thereof. The gaseous purging product on line 116 can be processed at least partially separated from one or more of several components therein.
[0015] Depending, at least in part, on the particular polymer product recovered via line 104 of the polymerization reactor 103, the composition of the gaseous product from the purge on line 116 can vary widely. The polymeric product in line 104 can be or include any desirable polymer or combination of polymers. For example, the polymeric product in line 104 can be or include one or more polyethylenes, polypropylenes, propylene copolymerized with ethylene, and the like. Preferably, the polymeric product includes copolymers of polyethylene and / or polyethylene. The term "polyethylene" refers to a polymer having at least 50% by weight of ethylene-derived units, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight, or at least at least 95% by weight or 100% by weight of ethylene-derived units. Polyethylene can therefore be homopolymers or copolymers, including a terpolymer, having one or more other monomer units or any combination thereof. As such, the polymeric product can include, for example, one or more olefins and / or α-olefin comonomers. Illustrative α-olefin comonomers may include, but are not limited to, those having 3 to approximately 20 carbon atoms, such as C3-C20 α-olefins, C3-C12 α-olefins or C3-C8 α-olefins. Suitable α-olefin comonomers can be linear or branched or can include two unsaturated carbon-carbon bonds (dienes). Two or more comonomers can be used. Examples of suitable comonomers may include, but are not limited to, linear C3-C12 α-olefins and α-olefins having one or more C1-C3 alkyl arms or an aryl group.
[0016] Various volatile hydrocarbons and / or other components contained in the gaseous purge product on line 116 may include, but are not limited to hydrogen, the purge gas (eg nitrogen), methane, any olefin monomer or combination of olefins including substituted and unsubstituted alkenes having two to 12 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-ene, 1- decene, 1-dodecene, 1-hexadecene and the like. The gaseous purging product on line 116 may also include one or more modifying components used in the polymerization of the olefin (s) as one or more inert hydrocarbons used as a gas phase solvent, muddy diluent or condensation agents (ICA). Illustrative inert hydrocarbons may include, but are not limited to, ethane, propane, butane, pentane, hexane, isomers thereof, derivatives thereof, or any combination thereof. The gaseous product from the purge can also include catalytic components such as alkyl aluminum compounds, such as triethyl aluminum (TEAL), aluminoxanes such as methylaluminoxane (MAO), tetraisobutyldialuminoxane (TIBAO), or any combination thereof.
[0017] The purge gas in line 112 can include any fluid or combination of fluids suitable for purification, that is, separation, at least a portion of the volatiles in the polymeric product to produce the polymeric product through line 117 having a reduced concentration of volatile as to the polymeric product in line 104. Illustrative purge gases may include, but are not limited to, nitrogen, argon, carbon monoxide, carbon dioxide, hydrocarbons such as ethylene and / or ethane or any combination thereof. In at least one example, the gaseous purging product on line 116 includes a mixture of the purging gas, for example, nitrogen, and volatiles removed from the polymeric product include ethylene, one or more ICAs and one or more α-olefin comonomers such as butene, hexene and / or octene.
[0018] The gaseous product of the purge on line 116 may be at a pressure ranging from approximately atmospheric pressure (approximately 101 kPa) to approximately 300 kPa, all pressures in this order are absolute pressure unless otherwise noted. For example, the purge gas pressure in line 116 can range from a decrease of approximately 101 kPa, approximately 105 kPa or approximately 110 kPa to an increase of approximately 150 kPa, approximately 200 kPa or approximately 250 kPa. In another example, the gaseous purging product on line 116 may be under a vacuum, that is, below atmospheric pressure. For example, the gaseous product from the purge on line 116 may be at a pressure ranging from a low of approximately 40 kPa, approximately 50 kPa or approximately 60 kPa to a high of approximately 70 kPa, approximately 80 kPa, approximately 90 kPa or approximately 100 kPa.
[0019] The gaseous product of the purge on line 116 can be at a temperature ranging from approximately ambient or atmospheric temperature (approximately 25 ° C) to approximately 120 ° C. For example, the temperature of the gaseous purging product on line 116 can range from a low of approximately 30 ° C, approximately 40 ° C, or approximately 50 ° C to a high of approximately 80 ° C, approximately 90 ° C, approximately 100 ° C, or approximately 110 ° C.
[0020] Depending on the temperature of the gaseous purging product in line 116, the gaseous purging product through line 116 can be introduced in one or more heat exchangers (one is shown 118), which can reduce the temperature of the same. For example, the gaseous product from the purge through line 116 and a heat transfer medium through line 114 can be introduced into the heat exchanger 118 where heat can be transferred indirectly from the purge gas to the heat transfer medium inside. of the heat exchanger 118 to produce a gaseous purge product cooled through line 120 and a heated heat transfer medium through line 119. The gaseous purge product in line 120 can be at a temperature of approximately 20 ° C to approximately 60 ° C. For example, the temperature of the gaseous purging product on line 120 may be less than approximately 55 ° C, less than approximately 45 ° C, less than approximately 40 ° C, less than approximately 35 ° C or less than approximately 30 ° C. Any suitable heat transfer means or combination of heat transfer means via line 114 may be introduced into heat exchanger 118. Illustrative heat transfer means may include, but are not limited to, water, air, one or more hydrocarbons , nitrogen, argon or any combination thereof. If a lower temperature is desired, one or more refrigeration systems can be used to reduce the temperature of the gaseous product from the purge to less than approximately 30 ° C. For example, refrigerant systems can reduce the temperature of the gaseous purging product in line 120 to a temperature of approximately 15 ° C or less, approximately 0 ° C or less, approximately -5 ° C or less, or approximately -15 ° C or less. Illustrative refrigerants may include, for example, hydrocarbons.
[0021] The gaseous product from the purge through line 120 can be introduced into a separator 121, which can separate at least a portion of any condensed fluid from the gaseous product from the purge. The condensed fluid separated through line 123 and the gaseous product of the purge through line 122 can be recovered from separator 121.
[0022] The gaseous purging product through line 122 can be introduced into a compression system 125 to produce a compressed gaseous purging product through line 149 and a recovered product, condensed through lines 133 and / or 148. The product purge gas compressed on line 149 can be at a pressure of approximately 2,500 kPa or more, approximately 2,700 kPa or more, approximately 2,900 kPa or more, approximately 3,200 kPa or more, approximately 3,500 kPa or more, approximately 3,700 kPa or more, approximately 3,900 kPa or more, approximately 4,100 kPa or more, approximately 4,300 kPa or more, approximately 4,500 kPa or more, approximately 5,000 kPa or more, approximately 7,000 kPa or more, approximately 8,000 kPa or more, approximately 9,000 kPa or more or approximately 10,000 kPa or more. For example, the gaseous product from the compressed purge on line 149 may be at a pressure ranging from a low of approximately 2,500 kPa, approximately 2,700 kPa, approximately 3,100 kPa, approximately 3,500 kPa, approximately 4,000 kPa or approximately 4,100 kPa to an increase of approximately 5,000 kPa, approximately 7,000 kPa, approximately 9,000 kPa or approximately 11,000 kPa. In another example, the gaseous product from the compressed purge on line 149 may be at a pressure of approximately 3,800 kPa to approximately 4,400 kPa or approximately 4,000 kPa to approximately 5,000 kPa or approximately 3,700 kPa to approximately 7,000 kPa, or approximately 4,000 kPa to approximately 4,700 kPa or approximately 2,500 to approximately 10,000.
[0023] During the compression of the gaseous purging product within the 125 compression system, the temperature of the gaseous purging product can be maintained below a predetermined maximum temperature. The maximum predetermined temperature can be based, at least in part, on the particular constitution or composition of the gaseous purging product in line 116. For example, if the gaseous purging product includes catalytic components such as triethyl aluminum (TEAL) and one or more olefins, the maximum predetermined temperature can be approximately 140 ° C because, if the gaseous product of the purge is heated to higher temperatures, polymerization can be initiated within the compression system. Depending, at least in part, on the particular composition of the gaseous purging product, for example, the presence of catalytic components and / or concentration of the catalytic component (s) in the gaseous purging product, the temperature of the gaseous purging product can be maintained below approximately 250 ° C, below approximately 225 ° C, below approximately 200 ° C, below approximately 175 ° C, below approximately 150 ° C, below approximately 140 ° C, below approximately 130 ° C, below approximately 120 ° C, below approximately 110 ° C, or below approximately 100 ° C, during compression.
[0024] The gaseous product of purging through line 116 may have a concentration of one or more catalytic components ranging from approximately 1 ppmp to approximately 500 ppmp. For example, the gaseous purging product on line 116 may have a concentration of one or more catalytic components ranging from a drop of approximately 1 ppmp, approximately 10 ppmp or approximately 25 ppmp to a rise of approximately 100 ppmp, approximately 150 ppmp, approximately 200 ppmp or approximately 250 ppmp. In another example, the purge compartment 115 can produce a gaseous purge product without or essentially without catalytic components, for example, less than approximately 1 ppmp, less than approximately 0.5 ppmp, or less than approximately 0.1 ppmp.
[0025] The gaseous purging product introduced through line 122 into the compression system 125 can be compressed in a plurality of compression stages or compressors. As shown in Figure 1, the compression system 125 includes three compressors or compression stages 128, 135 and 142 arranged in series relative to each other to produce the compressed purge gas product through line 149. In another example, the purge introduced through line 122 in compression system 125 can be compressed into two or more compressors or compression stages to produce the gaseous product from the compressed purge through line 149. Any number of compression stages can be used to produce the gaseous product of the compressed purge through line 149. For example, compression system 125 may include two compressors, three compressors, four compressors, five compressors, six compressors or seven compressors. Increasing the number of compressors or compression stages within the compression system 125 can reduce the rise in temperature of the gaseous purging product by each compression stage.
[0026] Compressors 128, 135, 142 can compress the gaseous purging product to any desired pressure ratio, i.e. any desired pressure ratio of the gaseous purging product introduced into a particular compressor compared to the pressure of the gaseous purging product pill recovered from that compressor. As a specific example, a gaseous purging product at a pressure of approximately 110 kPa introduced through line 122 into the compressor 128 and compressed at a pressure of approximately 385 kPa would have a pressure ratio of approximately 1: 3.5. Compressors 128, 135, 142 can compress the gaseous purging product in a pressure ratio ranging from a low of approximately 1: 2, approximately 1: 3, or approximately 1: 4 to a high of approximately 1: 5, approximately 1 : 6, approximately 1: 7, approximately 1: 8, approximately 1: 9, or approximately 1:10. In another example, compressors 128, 135, 142 can compress the gaseous product of the purge at a pressure ratio ranging from a drop of approximately 1: 2.5, approximately 1: 2.7, approximately 1: 3.0, approximately 1: 3.1, or approximately 1: 3.2 to an increase of approximately 1: 3.6, approximately 1: 3.8, approximately 1: 4.0, approximately 1: 4.5, approximately 1: 5, approximately 1: 5.5 , or approximately 1: 6. In another example, compressors 128, 135, 142 can compress the gaseous product from the purge at a pressure ratio of approximately 1: 3.2 to approximately 1: 3.6, approximately 1: 3.1 to approximately 1: 5, approximately 1: 3.2 to approximately 1: 4, approximately 1: 3.4 to approximately 1: 5, or approximately 1: 3.0 to approximately 1: 4. In another example, compressors 128, 135, 142 can compress the gaseous purging product in a pressure ratio of approximately 1: 3 to approximately 1: 6, approximately 1: 4 to approximately 1: 9, approximately 1: 5 to approximately 1: 9, approximately 1: 5 to approximately 1: 8, approximately 1: 6 to approximately 1: 8, or approximately 1: 4 to approximately 1: 8. The particular pressure ratio within each compressor 128, 135, 142 can be based, at least in part, on the desired pressure of the compressed purge gas product produced via line 149, the particular components contained in the purge gas product on line 116 , the type of the compressor, the desired maximum predetermined temperature of the compressed purge gas after any particular compressor or any combination thereof.
[0027] The compressor discharge temperature is directly related to the pressure proportion of the product purge gas introduced in a particular compressor or compression stage and the compressed purge gas product recovered from the compressor. As the gaseous purging product is compressed into the first, second, and third compressors 128, 135, 142 to produce the purging gaseous product through line 149, the partial pressure of monomers, for example, ethylene, increases. As such, the potential for polymerization initiation when one or more catalytic components such as TEAL are present in the gaseous product of the purge may increase. Thus, controlling the maximum temperature of the compressed purge gas recovered from each compressor or compression stage 128, 135, 142 may be desirable when the pressure increases. As such, the proportion of pressure at which the gaseous purge product is compressed within each compressor 128, 135, and 142 may be different from one another.
[0028] The first compressor 128 can compress the gaseous purging product introduced through line 122 in a pressure ratio equal to or greater than the second and third compressors 135, 142 compress the gaseous purging product. For example, the first compressor 128 can compress the gaseous purging product introduced via line 122 to it in a pressure ratio of at least 1: 3, at least 1: 3.5, at least 1: 4, at least 1 : 4.5, or at least 1: 5 and the second and third compressors can compress the gaseous product from the purge at a pressure ratio equal to or less than the first compressor 128. The first and second compressors 128, 135 can compress the product purge gas introduced through lines 122 and 134, respectively, at a pressure ratio equal to or greater than the third compressor 142 compresses the gaseous product from the purge introduced through line 141. As such, the pressure proportions at which the gaseous product of the purge is compressed within the first, second and third compressors 128, 135, 142 can decrease as the gaseous product of the purge is compressed within the compression system 125.
[0029] The maximum predetermined temperature of each compressed purge gas product recovered from compressors 128, 135, and 142 via lines 129, 136, and 143, respectively, can decrease as the pressure of the compressed purge gas product increases. In other words, the compressed purge gas product recovered through lines 129, 136, and 143 of each compressor 128, 135, 142, respectively, may have a different predetermined maximum temperature. The maximum predetermined temperature of the compressed purge gas product on line 129 can be equal to or greater than the maximum predetermined temperature of the purge purge product on line 136. Similarly, the maximum predetermined temperature of the compressed purge gas product on line 136 can be equal to or greater than the maximum predetermined temperature of the compressed purge gas product in line 143. For example, the maximum predetermined temperature of the compressed purge gas in line 129 can vary from approximately 125 ° C to approximately 150 ° C, the maximum predetermined temperature of the gas compressed purge gas in line 136 can range from approximately 115 ° C to approximately 130 ° C, and the maximum predetermined temperature of compressed purge gas in line 143 can vary from approximately 105 ° C to approximately 120 ° C. The particular predetermined maximum temperature of any particular compressed purge gas 129, 136, 143 may vary and may depend, at least in part, on the particular composition of the purge gas in line 116.
[0030] The compression system 125 may also include one or more heat exchangers and / or one or more separators that can cool and separate at least a portion of any condensed fluid from the compressed purge gas after one or more of the compression stages . As shown, the compression system 125 can include heat exchangers 130, 137, and 145 adapted to cool the compressed purge gas after each compression stage and separators 132, 139, and 147 that can separate at least a portion of any fluid condensate, if present, from the cooled compressed gaseous product recovered from heat exchangers 130, 137, 145, respectively. The compressed gaseous product recovered through line 129 of the first compressor 128 can be cooled within the heat exchanger 130 to produce a first compressed gaseous product cooled through line 131. The first compressed gaseous product cooled through the line 131 can be introduced into separator 132 to recover at least a portion of any condensed fluid through line 133 and a gaseous purge product through line 134. The gaseous purge product through line 134 can be compressed into compressor 135 and recovered through line 136 as a second gaseous product from the compressed purge. The second compressed gaseous product through line 136 can be introduced into heat exchanger 137 to produce a second compressed gaseous product cooled through line 138. The second compressed air gaseous product cooled through line 138 can be introduced into the separator 139 to recover at least a portion of any condensed fluid through line 140 and a gaseous purging product through line 141. The gaseous purging product via line 141 can be introduced into the third or final compressor 142 (as shown) for produce a third or final compressed gaseous product from the purge through line 143. The third compressed gaseous product from the line 143 can be introduced into heat exchanger 145 to produce the compressed gaseous product from a cooled third through line 146 The third cold compressed the gaseous purging product through line 146 can be introduced in separator 147 to recovering at least a portion of any condensed fluid through line 148 and the compressed gaseous purging product through line 149. Optionally, a portion of the compressed purging gaseous product through line 150 can be recovered from separator 147 and introduced into another separator 151. The separator 151 can further separate at least a portion of any condensed fluid that can be recovered through line 152 therefrom and a gaseous product from the purge through line 153. Separator 151 can also be configured or adapted to act as a vessel pressure. In other words, separator 151 can be configured or adapted to accommodate fluctuations or changes in the amount of the compressed purge gas product introduced to it via line 150. Separator 151 can also be configured or adapted to accommodate fluctuations or changes in an amount purging gas removed through line 153 of this. The gaseous product from the purge through line 153 can be recycled as auxiliary product discharge gas through line 107 to product discharge system 105. A constituent product discharge gas through line 154 can also be introduced into the gaseous product of purging on line 107. In another example, all or a portion of the gaseous product of purging on line 153 can be discharged from system 100, introduced into a firing system, introduced into a combustion device or system and consumed as fuel or any combination of them via line 155.
[0031] Heat exchangers 118, 130, and 137 can reduce the temperature of the compressed purge gas product prior to introduction for the first, second, and third compressors 128, 135, 142, respectively, by such an amount as to increase temperature associated with the compression of the gaseous purging product, and as such the temperature of the compressed purging gaseous product recovered from it can be controlled. For example, heat exchangers 118, 130, and 137 can reduce the temperature of the gaseous purging product introduced via lines 116, 129, and 136, respectively, such that the temperature of the gaseous purging product after each subsequent compression stage can be kept below approximately 250 ° C, below approximately 200 ° C, below approximately 150 ° C, below approximately 140 ° C, below approximately 130 ° C, below approximately 120 ° C, below approximately 115 ° C, below approximately 110 ° C, below approximately 105 ° C, or below approximately 100 ° C.
[0032] The temperature of the cooled gaseous purging products recovered through lines 120, 131, and 138, and 146 of heat exchangers 118, 130, 137, and 145, respectively, can be less than approximately 60 ° C, less than approximately 50 ° C, less than approximately 45 ° C, less than approximately 40 ° C, less than approximately 35 ° C, less than approximately 30 ° C, less than approximately 25 ° C, less than approximately 20 ° C, or less than approximately 15 ° C. For example, the temperature of the gaseous purging products cooled in lines 120, 131, 138, and 146 can vary from approximately 10 ° C to approximately 45 ° C, approximately 15 ° C to approximately 40 ° C, or approximately 15 ° C to approximately 35 ° C.
[0033] Additionally, when a portion of the gaseous purging product is condensed between two compressors, the interstage pressure will drop as the gaseous purging product condenses, which results in a lower pressure ratio of the previous compression stage and a proportion of higher compression of the subsequent compression stage. As such, the temperature of the downstream compression stage may increase due to condensation of the gaseous product from the compressed purge. Consequently, heat exchangers 118, 130 and / or 137 can be adapted to the compressed purge gas sufficiently fresh introduced thereto to maintain the temperature of the compressed purge gas recovered from each compressor 128, 135, 142 at a desired temperature.
[0034] The condensed fluid recovered through lines 123, 140, and 152 can be recycled to separator 132 and recovered as condensed fluid through line 133 thereof. The condensed fluid through line 133 can be introduced into one or more pumps 156 to produce a pressurized condensed fluid through line 157. In another example, the condensed fluid through lines 123, 140 and / or 152 can be directly combined with the condensate fluid in line 133. In another example, condensate fluid through lines 123, 140 and / or 152 can be introduced to separate pumps (not shown) to produce separate pressurized condensate fluids that can then be combined with the pressurized condensate fluid in the line 157.
[0035] Fluids condensed through line 133, 148, and 152 may include one or more of the heavier hydrocarbons contained in the gaseous purge product in line 116. For example, when the gaseous purge product in line 116 contains ethylene and a or more comonomers such as butene, hexene and / or octene, the major component (s) of condensed fluids in lines 133, 148 and / or 152 may include one or more comonomers. As used in this application, the term "main component" refers to a composition containing two or more components with the main component present in greater quantity. For example, the main component of a two-component composition would be present in an amount greater than 50%. In another example, the main component of a three-component composition can be present in an amount only approximately 34%, with the amount of the other two components each less than 34%, for example, approximately 33% more or less. When the gaseous purging product on line 116 contains ethylene and one or more inert hydrocarbons, for example, solvents, diluents or induced condensing agents (ICAs), such as propane, butane, pentane, hexane and / or octane, the component (s ) main of the condensed fluids in lines 133, 148 and / or 152 can be inert hydrocarbons. In another example, when the gaseous purging product in line 116 contains ethylene, one or more comonomers and one or more inert hydrocarbons, the main component (s) of the condensed fluids in lines 133, 148 and / or 152 may be the comonomer ( s) and inert hydrocarbons.
[0036] Depending, at least in part, on the particular composition of the gaseous purging product on line 116, the composition of the condensed fluids on lines 133, 148 and / or 152 can vary widely. When the gaseous product in the purge contains inert hydrocarbons, for example, isopentane, the concentration of inert hydrocarbons in lines 133, 148 and / or 152 can vary from a decrease of approximately 20% by weight, approximately 25% by weight or approximately 30% by weight to an increase of approximately 60% by weight, approximately 70% by weight, approximately 80% by weight, approximately 90% by weight or approximately 95% by weight. When the gaseous product in the purge contains comonomers, the concentration of comonomers, for example, butene, hexene and / or octene, can vary from a decrease of approximately 10% by weight, approximately 20% by weight or approximately 30% by weight to a high of approximately 40% by weight, approximately 50% by weight, approximately 60% by weight, approximately 70% by weight, approximately 80% by weight, approximately 90% by weight or approximately 95% by weight.
[0037] All or a portion of the pressurized condensate fluid in line 157 can be recycled through line 158 to polymerization reactor 103. In another example, all or a portion of the pressurized condensate fluid in line 157 can be removed via line 159 of polymerization system 100. For example, all or a portion of the condensed fluid pressurized through line 159 can be discharged, consumed, burned to generate heat, or otherwise disposed. In another example, a first portion of the pressurized condensate fluid on line 157 can be recycled via line 158 to polymerization reactor 103 and a second portion of the pressurized condensate fluid on line 157 can be removed via line 159 of polymerization system 100 As shown, the condensed fluid recovered through line 148 of separator 147 can be introduced through line 189 into the pressurized condensate fluid in line 158 and recycled to the polymerization reactor and / or introduced through line 188 into the pressurized condensate fluid in the line 159 and removed from polymerization system 100. Removing at least a portion of the pressurized condensed fluid through line 159 of polymerization system 100 can reduce the increase or accumulation of undesirable as inert compounds. Primary inert compounds that can be removed via line 159 may include, but are not limited to, hexane, butane, octane, 2-hexene, 3-hexene, and the like.
[0038] The amount of pressurized condensate fluid through line 159 removed from polymerization system 100 can range anywhere from approximately 1% to approximately 30% of the pressurized condensate fluid in line 157, which can also include any condensate fluid introduced through the line 188 of separator 147. For example, the amount of pressurized condensate fluid in line 157 and condensate fluid in line 148 removed through line 159 of polymerization system 100 can vary from a decrease of approximately 0.5%, approximately 1% or approximately 2% to an increase of approximately 5%, approximately 10%, approximately 20% or approximately 25%. Sometimes 100% of the pressurized condensate fluid in line 157 and the condensate fluid in line 148 can be recycled through line 158 to polymerization reactor 103. In another example, all or a portion of the condensed fluid through lines 123, 133 , 140, 148 and / or 152 can also be introduced in one or more of the compressors 128, 135 and / or 142. Introduce at least a portion of the condensed fluid through lines 123, 133, 140, 148 and / or 152 in one or more of the compressors 128, 134 and / or 142 can cause the condensed fluid to evaporate thereby reducing the temperature therein, thereby reducing the temperature of the compressed purging gas product recovered from it.
[0039] Reference again to the compressed purging gaseous product on line 143, at least a portion of the compressed purging gaseous product on line 143 can be recycled through line 144 to the purging gaseous product on line 116 before the first compressor 128. The compressed purge gas product through line 144 can be recycled continuously or periodically depending on the flow rate of the purge gas product through line 116. For example, a portion of the compressed purge gas product through line 144 can be periodically recycled to the gaseous product from the purge on line 116 such that a minimum fluid flow rate to the compression system 125 is maintained during the recovery process of typically periodic or cyclic polymeric product.
[0040] The gaseous product from the compressed purge through line 149 can be introduced into one or more refrigeration systems 160 to produce a plurality of products. The refrigeration system 160 can be a "self-cooling system" that uses the monomer as the refrigerant in a varied composition cycle. For example, refrigeration system 160 can produce a first product or "first recycle product" through line 174, a second product or "second recycle product" through line 178, and a third product or "third recycle product" "through line 185. As discussed and described in more detail below, the first, second and third products through lines 174, 178, and 185 can be portions or fractions of the compressed purge gas product on line 149. The first, second and third products through lines 174, 178, and 185 can be produced by cooling, separating and expanding the gaseous product from the compressed purge introduced through line 149 to the cooling system 160. As such, the refrigerant used within the cooling system 160 it can be the compressed purge gas product or at least one or more components contained in the compressed purge gas product. For example, methane, ethylene, ethane, propylene, propane, butene, butane, nitrogen, or any combination thereof, may be contained in the compressed purge gas and any one or more of these components may be used, alone or in any combination, such as the refrigerant within the refrigeration system 160. In another example, ethylene, ethane and nitrogen in the compressed purge gas product can make up a major part of the refrigerant used within the refrigeration unit 160.
[0041] The gaseous product from the compressed purge through line 149 can be introduced into a multi-stage refrigerator 161. The multistage cooler 161 can expand three or more portions of the compressed purge gaseous product, as described in more detail below, to produce a gaseous purge product cooled through line 162. Although not shown, the multistage cooler 161 can be replaced by a plurality of separate heat exchangers or a combination of separate and combined heat exchangers.
[0042] The gaseous product of the compressed purge cooled in line 162 may be at a temperature of approximately -60 ° C or less, approximately -65 ° C or less, approximately -70 ° C or less, approximately -75 ° C or less , approximately -80 ° C or less, approximately -85 ° C or less, approximately -90 ° C or less, or approximately -95 ° C or less. For example, the temperature of the compressed purge gas product cooled in line 162 can range from approximately -72 ° C to approximately -92 ° C, approximately -74 ° C to approximately -88 ° C, or approximately -76 ° C to approximately -86 ° C.
[0043] The gaseous product from the compressed purge cooled through line 162 can be introduced into one or more separators 163 to produce a gaseous product through line 164 and a condensed product through line 165. The gaseous product through line 164 can be introduced into one or more heat exchangers 166 to produce an additional cooled gaseous product through line 167. The cooled gaseous product in line 167 can be at a temperature of approximately -70 ° C or less, approximately -75 ° C or less, approximately -80 ° C or less, approximately -85 ° C or less, approximately -90 ° C or less, or approximately -95 ° C or less. The temperature of the gaseous product in line 167 can be reduced to 5 ° C, approximately 10 ° C, approximately 15 ° C, approximately 20 ° C, approximately 25 ° C, or approximately 30 ° C compared to the temperature of the gaseous product in line 164.
[0044] The gaseous product cooled through line 167 can be introduced in one or more separators 168 to produce a condensed product through line 169 and a gaseous product through line 170. The gaseous product through line 170 can be introduced in a first pressure reduction device 171 to produce a gaseous product extended through line 172. The pressure of the gaseous product extended through line 172 can be approximately 600 kPa or less, approximately 550 kPa or less, approximately 500 kPa or less, approximately 450 kPa or less, approximately 400 kPa or less or approximately 380 kPa or less. For example, the pressure of the gaseous product extended in line 172 can range from a drop of approximately 101 kPa, approximately 150 kPa or approximately 200 kPa to a rise of approximately 375 kPa, approximately 400 kPa or approximately 450 kPa. The temperature of the gaseous product extended in line 172 can be less than approximately -100 ° C, less than approximately -105 ° C, less than approximately -110 ° C, less than approximately - 120 ° C, less than approximately -125 ° C , or less than approximately - 130 ° C. For example, the temperature of the gaseous product extended in line 172 may be approximately -105 ° C to approximately -120 ° C, approximately -110 ° C to approximately -130 ° C, or approximately - 110 ° C to approximately - 140 ° C.
[0045] The gaseous product extended through line 172 can be introduced into the heat exchanger 166 where the heat can be indirectly transferred from the gaseous product introduced through line 164 to the extended gaseous product. A first product heated through line 173 can be recovered from heat exchanger 166 and introduced into the multistage heat exchanger 161 where heat can be transferred from the compressed purge gas product introduced through line 149 to the first heated product. As such, a first cooled compressed gaseous product can be produced by transferring the heat from the compressed purge gaseous product introduced through line 149 to the multistage heat exchanger 161 and a second first heated product through line 174 can be recovered. of the multi-stage heat exchanger 161. Depending, at least in part, on the temperature of the compressed purge gas product in line 149, the temperature of the second first product heated through line 174 can be approximately -20 ° C, approximately -10 ° C, approximately 0 ° C, approximately 20 ° C, approximately 30 ° C, or approximately 40 ° C. For example, the temperature of the first product through line 174 can vary from approximately 0 ° C to approximately 40 ° C, approximately 10 ° C to approximately 40 ° C, 20 ° C to approximately 40 ° C or approximately 25 ° C to approximately 35 ° C.
[0046] The refrigeration system or self-cooling system 160 can produce the first product through line 174 having a low concentration of heavy hydrocarbons, for example, C4, C5, C6, and C7 and heavier hydrocarbons. For a polyethylene-producing polymerization system 100, the first product in line 174 may include purging gas (eg nitrogen) as a major component and as minor components hydrogen and / or light hydrocarbons (eg hydrogen, methane , ethylene and ethane). For example, when the desired main component of the purge gas is nitrogen, the first product in line 174 may include approximately 70% by weight or more, approximately 75% by weight or more, approximately 80% by weight or more, approximately 85% by weight or more, approximately 90% by weight or more, or approximately 95% by weight or more of nitrogen. The combined concentration of other effective purge gas components such as hydrogen, methane, ethylene, and ethane, can vary from approximately 5% by weight to approximately 30% by weight. In another example, hydrogen, methane, ethane and / or ethylene may be the main component of the purge gas. The first product in line 174 may have a C4 hydrocarbon concentration of less than approximately 500 parts per million by volume (ppmv), less than approximately 400 ppm by volume, less than approximately 300 ppm by volume, less than approximately 200 ppm by volume , less than approximately 100 ppm by volume, less than approximately 75 ppm by volume, or less than approximately 50 ppm by volume. The first product in line 174 may have a C5 hydrocarbon concentration of less than approximately 250 ppm by volume, less than approximately 200 ppm by volume, less than approximately 150 ppm by volume, less than approximately 100 ppm by volume, less than approximately 50 ppm by volume, less than approximately 40 ppm by volume, less than approximately 30 ppmv, or less than approximately 20 ppm by volume. The first product in line 174 may have a C6 hydrocarbon concentration of less than approximately 75 ppm by volume, less than approximately 50 ppm by volume, less than approximately 30 ppm by volume, less than approximately 15 ppm by volume, less than approximately 10 ppmv, or less than approximately 5 ppm by volume. The first product in line 174 may have a concentration of C7 and heavier hydrocarbons of less than approximately 250 ppm by volume, less than approximately 200 ppm by volume, less than approximately 150 ppm by volume, less than approximately 100 ppm by volume, less approximately 50 ppm by volume, less than approximately 40 ppm by volume, less than approximately 30 ppm by volume, or less than approximately 20 ppm by volume.
[0047] Since the first product in line 174 includes a relatively high concentration of light components such as nitrogen and / or ethylene and a low concentration of heavier components, the first product recovered through line 174 of the various heat exchanger stages 161 can be recycled to the purge compartment 115 via line 112 as the purge gas. As such, the use of constituent gas or supplementary purge gas, such as nitrogen, can be reduced or eliminated and the purge gas through line 112 used to purge the volatile polymer product can be supplied from the first product in line 174. A portion of the first product in line 174 can be removed via line 175 of polymerization system 100 periodically or continuously. For example, the first product via line 175 can be discharged, consumed, burned to generate heat, or otherwise removed from polymerization system 100. A first portion of the first product on line 174 can be recycled via line 112 to the purge compartment 115 to supply at least a portion of the purge gas and a second portion of the first product on line 174 can be removed via line 175 of polymerization system 100.
[0048] The amount of the first product in line 174 that can be discharged, consumed, or otherwise removed from polymerization system 100 can vary from approximately 1% to approximately 30% of the first product in line 174. For example, the quantity of the first product in line 174 that can be removed via line 175 of polymerization system 100 can range from a decrease of approximately 0.5%, approximately 1% or approximately 2% to an increase of approximately 5%, approximately 10%, approximately 20% or approximately 25%. Sometimes, 100% of the first product on line 175 can be recycled via line 112 to purge compartment 115. Although not shown, at least a portion of the first product on line 174 can be recycled to compressor 128 via line 120 In another example not shown, the first product on line 175 can be compressed and introduced into the product discharge system 105 via line 107 to provide at least a portion of the product discharge auxiliary gas.
[0049] Removing at least a portion of the first product through line 175 of polymerization system 100 can mainly reduce the increase in purge gas, for example, nitrogen, within the compression and refrigeration systems 125, 160. Other components that can be discharged together with nitrogen may include mainly lighter hydrocarbons such as methane, ethane, ethylene, propane and / or propylene.
[0050] Referring again to the condensate product on line 165, a first portion of the condensate product on line 165 can be introduced into a second pressure reducing device 176 to produce an expanded or cooled product (second product) via line 177 The temperature of the second product in line 177 can be less than approximately -60 ° C, less than approximately -70 ° C, less than approximately -80 ° C, less than approximately -90 ° C, less than approximately -95 ° C , or less than approximately -100 ° C. For example, the temperature of the second product in line 177 can be approximately -60 ° C to approximately -110 ° C, approximately 65 ° C to approximately -90 ° C, or approximately 70 ° C to approximately -85 ° C .
[0051] When the polymeric product comprises polyethylene, the cooling system 160 can produce the second product through line 177 having a relatively high concentration of ethylene and ethane. For example, the combined concentration of ethylene and ethane in the second product in line 177 can be approximately 30% by weight or more, approximately 35% by weight or more approximately 40% by weight or more, approximately 45% by weight or more, approximately 50% by weight or more, approximately 55% by weight or more, approximately 60% by weight or more, approximately 65% by weight or more or approximately 70% by weight or more. The ethylene concentration in the second product in line 177 can range from a decrease of approximately 20% by weight, approximately 25% by weight or approximately 30% by weight to an increase of approximately 40% by weight, approximately 45% by weight, approximately 50% by weight or approximately 55% by weight. When butene is used as a comonomer in the production of polyethylene products, the second product in line 177 can also have a relatively high concentration of butene and / or butane. For example, the second product in line 177 may have a combined concentration of butene and butane ranging from a decrease of approximately 10% by weight, approximately 15% by weight or approximately 20% by weight to an increase of approximately 30% by weight, approximately 35% by weight or approximately 40% by weight. The concentration of butene in the second product in line 177 can range from a decrease of approximately 20% by weight, approximately 23% by weight or approximately 25% by weight to an increase of approximately 28% by weight, approximately 31% by weight or approximately 35% by weight. When hexene is used as a comonomer in the production of polyethylene products, the second product in line 177 may have a hexene concentration ranging from a drop of approximately 2% by weight, approximately 4% by weight or approximately 6% by weight to a high of approximately 10% by weight, approximately 12% by weight or approximately 14% by weight.
[0052] The second product through line 177 can be introduced into the multi-stage heat exchanger 161 where heat can be transferred from the compressed purge gas product introduced through line 149 to the second product. As such, the gaseous product from the compressed purge can be further cooled within the multistage heat exchanger 161 and a second product heated through line 178 can be recovered from it. Depending, at least in part, on the temperature of the compressed purge gas product in line 149, the temperature of the second product through line 178 can be approximately -20 ° C, approximately -10 ° C, approximately 0 ° C, approximately 20 ° C, approximately 30 ° C, or approximately 40 ° C. For example, the temperature of the second product through line 174 can vary from approximately 0 ° C to approximately 40 ° C, approximately 10 ° C to approximately 40 ° C, 20 ° C to approximately 40 ° C or approximately 25 ° C to approximately 35 ° C.
[0053] When the operating pressure of reactor 103 is less than the pressure of the condensate product in line 165, it may be advantageous to maintain the pressure of the second product recovered through line 178 above the reactor pressure to allow some or all of the second product to be recycled to reactor 103 through line 178 without requiring additional compression. The pressure of the second product in line 178 can range from a low of approximately 2,000 kPa, approximately 2,100 kPa or approximately 2,300 kPa to a high of approximately 2,400 kPa, approximately 2,700 kPa, approximately 3,000 kPa, approximately 3,500 kPa, approximately 4,100 kPa or approximately 4,900 kPa. Although not shown, one or more pumps can be used to increase the pressure of the condensate product in line 165 in order to increase the pressure of the second product recovered through line 178. For example, if the pressure inside reactor 103 is close or higher Since the pressure of the gaseous product from the compressed purge in line 149, the pressure of the condensed product in line 165 can be increased using one or more pumps in order to produce a second product through line 178 that can be directly recycled to reactor 103. Although not shown, all or a portion of the second product via line 178 can be introduced into the separation unit adapted to recover or separate an ethylene product from it.
[0054] A second portion of the condensed product on line 165 can be introduced through line 179 into a third pressure reducing device 180 to produce an expanded product through line 181. The pressure of the expanded product on line 181 can be approximately 600 kPa or less, approximately 550 kPa or less, approximately 500 kPa or less, approximately 450 kPa or less, approximately 400 kPa or less or approximately 380 kPa or less. For example, the pressure of the expanded product in line 181 can range from a drop of approximately 101 kPa, approximately 150 kPa or approximately 200 kPa to a rise of approximately 375 kPa, approximately 400 kPa or approximately 450 kPa. The temperature of the expanded product in line 181 can be less than approximately -60 ° C, less than approximately -70 ° C, less than approximately -80 ° C, less than approximately -90 ° C, less than approximately -95 ° C, or less than approximately -100 ° C. For example, the temperature of the expanded product in line 181 can vary from approximately -60 ° C to approximately -110 ° C, or from approximately -65 ° C to approximately -90 ° C, or from approximately -70 ° C to approximately - 85 ° C.
[0055] Referring again to the condensate product in line 169, the condensate product through line 169 can be introduced into a fourth pressure reduction device 182 to produce an expanded product through line 183. The pressure of the expanded product in the line 183 can be approximately 600 kPa or less, approximately 550 kPa or less, approximately 500 kPa or less, approximately 450 kPa or less, approximately 400 kPa or less or approximately 380 kPa or less. For example, the pressure of the expanded product in line 183 can range from a drop of approximately 101 kPa, approximately 150 kPa or approximately 200 kPa to a rise of approximately 375 kPa, approximately 400 kPa or approximately 450 kPa. The temperature of the expanded product in line 183 can be less than approximately -60 ° C, less than approximately -70 ° C, less than approximately -80 ° C, less than approximately -90 ° C, less than approximately -95 ° C, or less than approximately -100 ° C. For example, the temperature of the expanded product in line 183 can be approximately -60 ° C to approximately -110 ° C, approximately -65 ° C to approximately -90 ° C, or approximately - 70 ° C to approximately -85 ° C.
[0056] The expanded product on line 183 and the expanded product on line 181 can be combined together to produce an expanded or cooled product (third product) via line 184. The third product cooled through line 184 can be introduced into the exchanger multistage heat exchanger 161 where heat can be transferred from the compressed purge gas product introduced through line 149 into the third cooled product. As such, the gaseous product from the compressed purge can be further cooled within the multistage heat exchanger 161 and a third product heated through line 185 which includes the products expanded in lines 181 and 183 can be recovered from the heat exchanger of several stages 161. Depending, at least in part, on the temperature of the compressed purge gas product in line 149, the temperature of the third product through line 185 can be approximately -20 ° C, approximately -10 ° C, approximately 0 ° C, approximately 20 ° C, approximately 30 ° C, or approximately 40 ° C. For example, the temperature of the third product through line 185 can vary from approximately 0 ° C to approximately 40 ° C, approximately 10 ° C to approximately 40 ° C, 20 ° C to approximately 40 ° C or approximately 25 ° C to approximately 35 ° C.
[0057] When polymerization system 100 produces polyethylene products, cooling system 160 can produce a third product via line 185 having a relatively high concentration of ethylene. At least a portion of the third product in line 185 can be recycled through line 186 to the gaseous product of the purge in line 116 or 120. When polymerization system 100 produces polyethylene polymers, the third product in line 185 can have a concentration ethylene of approximately 20% by weight or more, approximately 25% by weight or more, approximately 30% by weight or more approximately 35% by weight, or more, approximately 40% by weight or more, approximately 45% by weight or more , approximately 50% by weight or more, approximately 55% by weight or more or approximately 60% by weight or more. The third product in line 185 may have an ethane concentration ranging from a decrease of approximately 10% by weight, approximately 15% by weight or approximately 20% by weight to an increase of approximately 25% by weight, approximately 30% by weight, approximately 35% by weight or approximately 40% by weight. When butene is used as a comonomer in the production of polyethylene, the third product in line 185 may have a concentration of butene ranging from a low of approximately 5% by weight, approximately 10% by weight or approximately 15% by weight to a high of approximately 20% by weight, approximately 25% by weight or approximately 30% by weight. The concentration of other C4 hydrocarbons can vary from a decrease of approximately 1% by weight, approximately 2% by weight or approximately 3% by weight to an increase of approximately 4% by weight, approximately 5% by weight or approximately 6% by weight .
[0058] At least a portion of the third product on line 185 can be removed via line 187 of polymerization system 100. For example, at least a portion of the third product via line 187 can be discharged, consumed, burned to generate the heat, or otherwise removed from polymerization system 100. In at least one example, a first portion of the third product via line 186 can be recycled to the gaseous purging product on line 116 or 120 and a second portion of the third product through line 187 can be removed from polymerization system 100. Removing at least a portion of the third product through line 187 from polymerization system 100 can reduce the concentration of unwanted components which thereby reduces and / or prevents the increase of components unwanted components in the polymerization system 100. The unwanted components that can be removed from the polymerization system 100 by removing at least a portion of the third pr oduct through line 187 of these may include, but are not limited to, inert compounds such as methane, ethane, propane, butane and combinations thereof.
[0059] The amount of the third product removed through line 187 of polymerization system 100 can vary anywhere from 1% to approximately 50% of the third product in line 185. For example, the amount of the third product removed through line 187 of the polymerization system 100 can range from a low of approximately 1%, approximately 3% or approximately 5% to a high of approximately 10%, approximately 15%, approximately 20%, approximately 25% or approximately 30%. Sometimes, 100% of the third product on line 185 can be recycled via line 186 to the gaseous product from the purge on line 116. Although not shown, in another example, the entire third product on line 185 can be recycled via line 186 for the gaseous purging product on line 116 or 120 and a portion of the second product on line 178 can be discharged, consumed, burned to generate heat, or otherwise removed from polymerization system 100 to reduce the increase in unwanted components in the system of polymerization 100. In another example, a portion of the third product via line 186 and a portion of the second product on line 178 can be discharged from polymerization system 100.
[0060] Heat exchangers 118, 130, 137, 145, 161, and 166 can be or include any system, device or combination of systems and / or devices suitable for indirectly transferring heat from one fluid to another fluid. For example, heat exchangers can be or include one or more shell-tube heat exchangers, plate and frame, plate and fin, spiral-wound, coil-wound, U-tube and / or bayonet style. In one or more embodiments, one or more heat exchangers may also include tubes with enlarged surface (eg fins, static mixers, rifling, conductive heat packaging, turbulence-causing projections or any combination thereof), and the like. Although not shown, one or more heat exchangers 118, 130, 137, 145, 161, and 166 can include a plurality of heat exchangers. If a plurality of heat exchangers are used for any one or more of the heat exchangers 118, 130, 137, 145, 161, and 166, the heat exchangers can be of the same or different types.
[0061] The separators 121, 132, 139, 147, 151, 163, and 168 can be or include any system, device or combination of systems and / or devices suitable for separating gas from liquids. For example, separators can be or include one or more flash tanks, distillation columns, fractionation columns, split-wall columns or any combination thereof. Separators may contain one or more internal structures including, but not limited to trays, random packaging elements such as rings or saddles, structured packaging or any combination thereof. Separators can be or include an open column with no internal elements. The separators can be a partially empty column containing one or more internal structures.
[0062] Compressors 128, 135, 142 can include any type of compressor. Illustrative compressors may include, but are not limited to, axial compressors, centrifugal compressors, rotary positive displacement compressors, diagonal or variable flow compressors, reciprocating compressors, dry screw compressors, oil flooded screw compressors, roller compressors and similar. Compressors 128, 135, 142 can be separate compressors or a single compressor that has three or more stages of compression. Compressors 128, 135, 142 can be driven by a single or common motor, separate motors or a combination thereof. Compressors 128, 135, 142 can be of the same or different type of compressor. For example, compressors 128, 135, 142 can all be reciprocating compressors. In another example, the first compressor 128 can be a dry screw compressor and the second and third compressors 135, 142 can be reciprocating compressors.
[0063] Pressure reduction devices 171, 176, 180 and 182 can be or include any system, device or combination of systems and / or devices suitable for reducing pressure adiabatically or substantially adiabatically a compressed fluid. Illustrative pressure reducing devices may include, but are not limited to, valves, nozzles, orifices, porous plugs and the like.
[0064] Figure 2 represents a schematic diagram of an illustrative compression system 200 for compressing the gaseous purging product on line 116. The compression system 200 may be similar to the compression system 125 discussed and described above with reference to Figure 1 The compression system 200 may further include a line 205 of gaseous product from the compressed recycle purge instead of or in addition to the recycle line 144 (see Figure 1).
[0065] The compression system 200 shown in Figure 2 is configured to increase the initial compressor volumes, that is, to increase the pressure ratio of the gaseous product of the compressed purge in an upstream compression stage in relation to a compression stage thereafter, thereby reducing the temperature of the gaseous product from the purging then compressed. In other words, the compression system 200 can provide a maximum pressure ratio to which the gaseous purging product is subjected during compression at each stage by recycling a portion of the compressed purging product on line 205 to the compressed purging gas in the line 129 and for compressed purge gas on line 136. As such, the pressure ratio of the compressed purge gas product recovered from each compressor 128, 135, 142 can be prevented from exceeding a predetermined pressure ratio of a compression stage in particular, thereby fixing or substantially fixing the maximum discharge temperature of compressed purge gas recovered from compressors 128, 135, 142.
[0066] A first portion of the compressed purge gas product on line 205 can be recycled through line 215 to the compressed purge gas product on line 129 recovered from the first compressor 128. A second portion of the compressed purge gas product on line 205 can be recycled through line 210 for the compressed purge gas product in line 136 recovered from the second compressor 135. Although not shown, a third portion of the compressed purge gas product through line 144 (see Figure 1) can be recycled to the gaseous purging product on line 116.
[0067] The amount of the compressed purge gas product in line 143 that can be recycled via lines 210, 215 and / or 144 can vary widely depending on the particular flow rate of the purge gas product introduced through line 116 in the compression 200. The amount of the compressed purge gas product recycled through lines 210, 215 and / or 144 can be adjusted to maintain a desired pressure ratio to which the purge gas product is subjected within each compressor 128, 135, 142 such that the temperature of the compressed purge gas recovered from each compressor is maintained below the predetermined maximum temperature.
[0068] Figure 3 represents a schematic diagram of an illustrative compression system 300 for compressing the gaseous purging product on line 116. The compression system 300 may be similar to the compression system 125 discussed and described above with reference to Figure 1 The compression system 300 may further include the gaseous product recycle lines from the compressed purge 305, 310, and 315 instead of or in addition to the recycle line 144 shown in Figure 1.
[0069] As shown, a portion of the gaseous purging product compressed on lines 129, 136, and 143 recovered from the first, second and third compressors 128, 135, and 142, respectively, can be recycled to the upstream purging product. compressor through lines 305, 310 and 315, respectively. As discussed above, the gaseous purging product can be kept at a predetermined maximum temperature or below during compression and recycling a portion of the compressed purging gaseous product after each compression stage can provide control in adjusting the temperature of the gaseous product of the compressed purge after each compression stage 128, 135, 142.
[0070] As shown in Figure 3, a portion of the compressed purge gas recovered from each compressor 128, 135, 142 can be recycled at the inlet of each compressor to provide a desired pressure ratio for each compressor. The desired pressure ratio of each compressor 128, 135, 142 can be determined, at least in part, based on the desired discharge temperature of each compressor of a particular composition of the gaseous product in the purge. Additionally, instead of recycling a portion of the compressed purge gas product through line 144 to the purge gas product on line 116 (as shown in Figure 1) or recycling a portion of the purge gas product on line 143 through lines 210 and 215 for the compressed purge gas product on lines 129 and 136 (as shown in Figure 2) a portion of the compressed purge gas product recovered via lines 129, 136, and 143 from each compressor 128, 135, and 142, respectively , can be recycled to the gaseous product of the previous purge before being introduced into the compressor. For example, a portion of the compressed purge gas product on line 129 can be recycled via line 305 to the purge gas purge product on line 116. A portion of the compressed purge gas product on line 136 can be recycled via line 310 to the compressed purge gas product in line 129. A portion of the compressed purge gas product in line 143 can be recycled via line 315 to the compressed purge gas product in line 136. Recycle a portion of the compressed purge gas product in line 129 129, 136, and 143 through lines 305, 310, and 315, respectively, for the gaseous purging product on lines 116, 129 and 136, respectively, can result in a reduced or lower flow rate through the later compression stages because the recycle flows are not composed from stage to stage. In addition, recycling the compressed gaseous purging products through lines 305, 310, and 315 can reduce total energy consumption because less gaseous purging product is compressed by the compression stages.
[0071] Figure 4 represents a schematic diagram of an illustrative polymerization system 400 for producing one or more polymer products and recovering volatiles from them. The polymerization system 400 can include the polymerization reactor 103; product discharge system 105; purge compartment 115; heat exchangers 118, 130, and 145; separators 121, 132, 147 and 151; and cooling system 160, as discussed and described above with reference to Figure 1. Instead of having three compressors 128, 135, and 142, however, polymerization system 400 may include a compression system 405 having two compressors 407, 425 The gaseous product of purging through line 116, if desired, can be introduced into heat exchanger 118 and separator 121 to separate at least a portion of any condensed fluid through line 123 and supply the gaseous product of purging through line 122, as discussed and described above with reference to Figure 1.
[0072] The gaseous purging product through line 122 can be introduced into the 405 compression system to produce a compressed purging gaseous product through line 149 and a recovered product, condensed through lines 133 and / or 148. The gaseous product of the compressed purge at line 149 can be as discussed and described above with reference to Figure 1. For example, the gaseous purge product compressed at line 149 can be at a pressure ranging from a low of approximately 2,500 kPa, approximately 2,700 kPa, approximately 3,100 kPa, approximately 3,500 kPa, approximately 4,000 kPa or approximately 4,100 kPa at an increase of approximately 5,000 kPa, approximately 6,000 kPa, approximately 7,000 kPa, approximately 8,000 kPa, approximately 9,000 kPa or approximately 10,000 kPa. Depending, at least in part, on the particular composition of the gaseous purging product, for example, the presence of catalytic components and / or the concentration of the catalytic component (s) in the gaseous purging product, the temperature of the gaseous purging product can be kept below approximately 250 ° C, below approximately 225 ° C, below approximately 200 ° C, below approximately 175 ° C, below approximately 150 ° C, below approximately 140 ° C, below approximately 130 ° C, below approximately 120 ° C, below approximately 110 ° C, or below approximately 100 ° C during compression.
[0073] Compressors 407 and 425 can compress the gaseous product of the purge at any desired pressure ratio. For example, compressors 407 and 425 can compress the gaseous product from the purge at a pressure ratio ranging from a low of approximately 1: 2, approximately 1: 3, or approximately 1: 4 to a high of approximately 1: 5, approximately 1: 6, approximately 1: 7, approximately 1: 8, approximately 1: 9, or approximately 1:10. In another example, compressors 407 and 425 can compress the gaseous product from the purge at a pressure ratio of approximately 1: 3 to approximately 1: 6, approximately 1: 4 to approximately 1: 9, approximately 1: 5 to approximately 1: 9, approximately 1: 5 to approximately 1: 8, approximately 1: 6 to approximately 1: 8, or approximately 1: 4 to approximately 1: 8. The particular proportion of pressure within each compressor 407 and 425 can be based, at least in part, on the desired pressure of the compressed purge gas product produced via line 149, the particular components contained in the purge gas product on line 116, the compressor type, the maximum desired predetermined temperature of the compressed purge gas after any particular compressor or any combination thereof.
[0074] The proportion of pressure at which the gaseous product of the purge is compressed within each compressor 407, 425 can be the same or different. Compressor 407 can compress the gaseous purging product at a pressure ratio equal to or greater than compressor 425. For example, compressor 407 can compress the gaseous purging product introduced through line 122 to this at a pressure ratio of approximately 1: 6 or more, approximately 1: 6.5 or more, approximately 1: 7 or more, approximately 1: 7.5 or more, approximately 1: 8 or more, or approximately 1: 8.5 or more and the compressor 425 can compress the gaseous purging product at a pressure ratio equal to or less than the first compressor 407. Compressor 407 can compress the gaseous purging product at a pressure ratio equal to or less than the compressor 425. For example, the first compressor can compress the purge gas introduce through line 122 to that in a pressure ratio of approximately 1: 3 or less, approximately 1: 4 or less, approximately 1: 5 or less, approximately 1: 6 or less, approximately 1 : 7 or less, or closer 1: 8 or less and the second compressor 425 can compress the gaseous product at a pressure ratio equal to or greater than the first compressor 407. Compressor 407 can compress the gaseous product at approximately the same pressure ratio as the compressor 425. For example, compressors 407 and 425 can each compress the gaseous product of the purge introduced to it in a pressure ratio of approximately 1: 5, approximately 1: 5.5, approximately 1: 6, approximately 1: 6.5, approximately 1: 7, approximately 1: 8, approximately 1: 8.5, or approximately 1: 9.
[0075] The gaseous product of the compressed purge recovered through lines 410 and 143 can have the same predetermined or different maximum temperature. The maximum predetermined temperature of the compressed purge gas in line 410 can be equal to or greater than the maximum predetermined temperature of the purge gas in line 143. For example, the maximum predetermined temperature of the compressed purge gas in line 410 can vary from approximately 125 ° C to approximately 250 ° C and the maximum predetermined temperature of the compressed purge gas in line 143 can vary from approximately 105 ° C to approximately 200 ° C. The particular predetermined maximum temperature of any particular compressed purge gas via lines 410 and 143 can vary widely and may depend, at least in part, on the composition of the particular purge gas in line 116.
[0076] The 405 compression system can also include one or more heat exchangers and / or one or more separators that can cool and separate at least a portion of any condensed fluid from the compressed purge gas after one or both of the compression stages 407, 425. As shown, the compression system 405 includes heat exchangers 130 and 145 that can be adapted to cool the compressed purge gas after each compression stage 407 and 425 and separators 132 and 147 that can separate at least one portion of any condensed fluid, if present, of the cooled compressed gaseous product recovered via lines 133 and 148 of heat exchangers 130 and 145, respectively, as discussed and described above with reference to Figure 1. For example, the gaseous product of the compressed purge recovered through line 415 of the first compressor 405 can be cooled inside the heat exchanger 130 to produce a first gaseous product of the compressed purge cools through line 415. The first compressed purge gaseous product cooled through line 415 can be introduced into separator 132 to recover at least a portion of any condensed fluid through line 133 and a gaseous purge product through line 420. The gaseous purging product through line 420 can be compressed within the second compressor 425 and the gaseous purging product compressed through line 143 can be recovered therefrom. The gaseous purging product through line 143 can be introduced into heat exchanger 145 to produce a gaseous purging product cooled through line 146. The gaseous purging product cooled through line 146 can be introduced into separator 147 to recover at least a portion of any condensed fluid through line 148 and the gaseous purging product compressed through line 149. Optionally, a portion of the gaseous purging product through line 150 can be recovered from separator 147 and introduced into another separator 151 as discussed and described above with reference to Figure 1 to produce the condensate fluid through line 152 and / or the gaseous product of the purge through line 153. The condensate fluid recovered through lines 123 and / or 152 can be recycled to separator 132 and recovered this through line 133.
[0077] Heat exchangers 118 and 130 can reduce the temperature of the gaseous product in the purge before introduction to the first and second compressors 407 and 425, respectively, by a sufficient amount such that the temperature increase associated with the compression of the gaseous product of the purge within each compressor 407 and 425, and the temperature of the compressed purge gas recovered from it can be controlled. For example, heat exchangers 118 and 130 can reduce the temperature of the gaseous purging product introduced via lines 116 and 410, respectively, such that the temperature of the gaseous purging product after each subsequent compression stage is kept below approximately 250 ° C, approximately 225 ° C, approximately 200 ° C, approximately 175 ° C, approximately 150 ° C, approximately 140 ° C, approximately 130 ° C, approximately 120 ° C, approximately 115 ° C, approximately 110 ° C, approximately 105 ° C, or approximately 100 ° C.
[0078] The temperature of the cooled gaseous purge products recovered through lines 120, 415, and 146 of heat exchangers 118, 130, and 145, respectively, can be less than approximately 60 ° C, less than approximately 50 ° C, less than approximately 45 ° C, less than approximately 40 ° C, less than approximately 35 ° C, less than approximately 30 ° C, less than approximately 25 ° C, less than approximately 20 ° C, or less than approximately 15 ° C. For example, the temperature of the gaseous purging products cooled in lines 120, 415, and 146 can vary from approximately 10 ° C to approximately 45 ° C, approximately 15 ° C to approximately 40 ° C, or approximately 15 ° C to approximately 35 ° C. If a refrigeration system is used to cool the gaseous purging products on lines 116, 410 and / or 143, the temperature of the gaseous purging products recovered through lines 120, 415 and / or 146 can be approximately 15 ° C or less , approximately 5 ° C or less, approximately 0 ° C or less, approximately -10 ° C or less, or approximately -15 ° C or less.
[0079] As shown, a portion of the condensed fluid in lines 133 and / or 148 can be recycled downstream to compressors 407 and 425, respectively. For example, a portion of any condensate fluid on line 133 can be recycled through line 417 to the first compressor 407. Introducing a portion of the condensed fluid through line 417 to compressor 407 can cool the compressed purge gas product through line 410 recovered from this. For example, the condensed fluid can be introduced into compressor 407 and can be expanded therein which can remove heat from the compressed purge gas inside compressor 407. Similarly, a portion of the condensed fluid in line 148 can be recycled through line 423 to the second compressor 425. Although not shown, the condensed fluid recycled through lines 417 and / or 423 can be introduced into the gaseous product of the purge in lines 122 and / or 420. For example, the condensed fluid can be introduced into the gaseous product of the purge on lines 122 and / or 420 as an atomized liquid.
[0080] The compressed purge gas product recovered through line 149 of compression system 405 can be introduced into the cooling system 160 and processed to produce the first, second and third products through lines 174, 178, and 185 as discussed and described above with reference to Figure 1. Fluid condensed through line 133 can be introduced into pump 156 to produce condensed fluid pressed through line 157 that can be recycled to polymerization reactor 103 through line 158 and / or removed from the polymerization system 400 through line 159. In addition, the condensate fluid through line 148 recovered from separator 147 can be introduced into the pressurized condensate fluid in line 158 and recycled to polymerization reactor 103 and / or pressurized condensate fluid in line 159 and removed from the polymerization system 400.
[0081] Compressors 407 and 425 can include any type of compressor. Illustrative compressors may include, but are not limited to, axial compressors, centrifugal compressors, rotary positive displacement compressors, variable or diagonal flow compressors, dry screw reciprocating compressors, oil flooded screw compressors, roller compressors and the like. Compressors 407 and 425 can be driven by a single motor (not shown) or separate motors (not shown). Compressors 407 and 425 can be separate compressors or a single compressor that has two stages of compression. Compressors 407, 425 can be of the same type of compressor or of different types of compressors. For example, the first compressor 407 and the second compressor 425 can both be dry screw compressors. In another example, the first compressor 407 can be a dry screw compressor and the second compressor 425 can be a reciprocating compressor.
[0082] Figure 5 represents a schematic diagram of an illustrative gas phase polymerization system 500 for the production of polymers. The gas phase polymerization system 500 can be used to produce the polymeric product via line 104 and the gaseous purging product via line 116 discussed and described above with reference to Figures 1-4. The polymerization system 500 can include one or more polymerization reactors 103, product discharge systems 105, purge compartments 115, recycle compressors 570, and heat exchangers 575. The polymerization system 500 can include more than one reactor 103 arranged in series, parallel or configured independently from other reactors, each reactor having its own associated discharge tanks 105, recycle compressors 570, and heat exchangers 575, or alternatively, sharing one or more of the associated discharge tanks 105, compressors of recycle 570, and heat exchangers 575. For simplicity and ease of description, the modalities of the invention will be described further in the context of a single reactor train.
[0083] A plurality of reactors 103, however, can be used to produce a plurality of polymer products, from which at least a portion of the volatile components thereof can be removed via one or more product discharge systems 105 and one or further purge compartments 115 to produce a plurality of gaseous purge products or a single gaseous purge product derived from a plurality of polymer products. For a plurality of polymerization systems 500, multiple gaseous purging products recovered from these can be combined into a single gaseous purging product which can then be introduced into the compression system 125, 200, 300, or 405 and cooling system 160 to separate the gaseous product of the purge combined into multiple components, as discussed and described above with reference to Figures 1-4. For example, two polymerization reactors 103 can be used to produce two different polyethylene products through lines 104 of these. Two different polyethylene products can be produced using different catalysts, ICAs, comonomers and the like. The compression system 125, 200, 300, or 405 and / or cooling system 160 can be configured to separate different ICAs and / or different comonomers from each other. At least a portion of separate ICAs and different comonomers can be recycled to their respective polymerization reactors 103. As such, compression system 125, 200, 300, or 405 and / or cooling system 160 can be used to separate and recycling various components of multiple gaseous purging products having different compositions for their respective polymerization reactors 103, thereby reducing the number of purging gas recovery systems required to separate gaseous purging products recovered from multiple polymerization systems.
[0084] When multiple gaseous purging products are recovered from multiple polymer products, the composition of the gaseous purging products may be different. For example, an ethylene / butene copolymer product produced using isopentane as an ICA can produce a gaseous purge product containing ethylene, butene and isopentane. An ethylene / hexene copolymer produced using hexane as an ICA can produce a gaseous purge product containing ethylene, hexene and hexane. When those gaseous purging products having different compositions are combined and introduced in the compression system 125, 200, 300, or 405 and later in the cooling system 160, several components can be separated or at least partially separated from each other with compression system 125, 200, 300, or 405 and / or refrigeration 160. For example, separators 121, 132, 139, 147, and 151 and their operating conditions can be configured such that a particular component or components of the gaseous product in the purge condensate introduced in these can be recovered from these. As such, condensed products recovered via lines 123, 140, 152 and / or 148 can be recovered as separate products from separators 121, 139, 147, and 151, respectively, and recycled to the appropriate position in their respective polymerization system. . To improve the separation of various components, separators 121, 132, 139, 147 and / or 151, as discussed above, can include protrusions, packaging material, trays, dividing walls, and the like in order to improve or increase the separation of different components in the condensed products introduced in them. Similarly, separators 163 and 168 can be adapted to separate multiple condensed and / or gaseous components introduced therein.
[0085] Reactor 103 may include cylindrical section 503, transition section 505, and a speed reduction zone or dome or "upper head" 507. The cylindrical section 503 is arranged adjacent to the transition section 505. The transition section 505 can expand from a first diameter corresponding to the diameter of the cylindrical section 503 to a larger diameter adjacent to the dome 507. The position or connection in which the cylindrical section 503 connects to the transition section 505 can be referred to like the "neck" or the "reactor neck" 504.
[0086] The cylindrical section 503 can include a reaction zone 512. The reaction zone can be a fluidized reaction bed or fluidized bed. In one or more embodiments, a distributor plate 519 can be arranged within cylindrical section 503, generally at the end of the cylindrical section or towards it which is in front of the end adjacent to the transition section 505. Reaction zone 512 may include a bed of growing polymer particles, polymer particles formed, and the catalyst particles fluidized by the continuous flow of polymerizable gaseous components and modifiers in the form of constituent feed and recycle the fluid through reaction zone 512.
[0087] One or more cycle fluid lines 515 and discharge lines 518 may be in fluid transmission with the dome 507 of the reactor 103. The polymeric product can be recovered through line 104 of the reactor 103. A feed from the reactor via line 101, it can be inserted into the polymerization system 500 in any position or combination of positions. For example, reactor supply through line 101 can be introduced into cylindrical section 503, transition section 505, speed reduction zone 507, anywhere within the cycle fluid line 515, or any combination thereof . Preferably, the reactor feed 101 is introduced into the cycle fluid in line 515 before or after heat exchanger 575. The catalyst feed through line 102 can be introduced into the polymerization system 500 at any point. Preferably, the catalyst feed through line 102 is introduced into a fluidized bed 512 within cylindrical section 503.
[0088] In general, the height to diameter ratio of cylindrical section 503 can vary in the range of approximately 2: 1 to approximately 5: 1. The range, of course, can vary to a greater or lesser extent and depends, at least in part, approximately on the desired production capacity and / or dimensions of the reactor. The cross-sectional area of the dome 507 is typically within the range of approximately 2 to approximately 3 multiplied by the cross-sectional area of the cylindrical section 503.
[0089] The speed reduction or dome zone 507 has a larger inner diameter than the cylindrical section 503. As the name suggests, the speed reduction zone 507 reduces the gas speed due to the increased cross-sectional area. This reduction in gas velocity allows particles captured in the rising mobile gas to recede in the bed, leaving mainly only the gas at the outlet above the reactor 103 through the cycle fluid line 515. The cycle fluid recovered through the line 515 may contain less than approximately 10% by weight, less than approximately 8% by weight, less than approximately 5% by weight, less than approximately 4% by weight, less than approximately 3% by weight, less than approximately 2% by weight, less than approximately 1% by weight, less than approximately 0.5% by weight, or less than approximately 0.2% by weight of the particles captured in the fluidized bed 512. In another example, the cycle fluid recovered through line 515 may have a particle concentration ranging from a drop of approximately 0.001% by weight to approximately 5% by weight, from approximately 0.01% by weight to approximately 1% by weight, or from approximately 0.05% by weight to approximately 0.5% by weight, based on pe total particle fluid / cycle mixture in line 515. For example, the particle concentration in the cycle fluid in line 515 can range from a decrease of approximately 0.001% by weight, approximately 0.01% by weight, approximately% 0.05% by weight, approximately 0.07% by weight or approximately 0.1% by weight at an increase of approximately 0.5% by weight, approximately 1.5% by weight, approximately 3% by weight or approximately 4 % by weight, based on the total weight of the cycle fluid and particles in line 515.
[0090] Gas phase polymerization processes, suitable for production of polymeric product, for example, a polymeric polyethylene product, through line 104 are described in U.S. Patent Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,588,790; 4,882,400; 5,028,670; 5,352,749; 5,405,922; 5,541,270; 5,627,242; 5,665,818; 5,677,375; 6,255,426; European Patent Nos. EP 0802202; EP 0794200; EP 0649992; EP 0634421. Other suitable polymerization processes that can be used to produce the polymeric product may include, but are not limited to, high pressure solution, slurry and polymerization processes. Examples of slurry solution or polymerization processes are described in U.S. Patent Nos. 4,271,060; 4,613,484; 5,001,205; 5,236,998; and 5,589,555.
[0091] As noted above, the reactor supply on line 101 can include any polymerizable hydrocarbon from the hydrocarbon combination. For example, the reactor feed can be any olefin monomer including substituted and unsubstituted alkenes having two to 12 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 4-methylpent-1-ene, 1-decene, 1-dodecene, 1-hexadecene, and the like. The reactor supply on line 101 may also include non-hydrocarbon gas (aces) such as nitrogen and / or hydrogen. The reactor supply through line 101 can enter the reactor in multiple and different positions. For example, the reactor feed through line 101 can be introduced into fluidized bed 512 in several ways including direct injection through a nozzle (not shown) into the fluidized bed. The polymeric product in line 104 can thus be a homopolymer or a copolymer, including a terpolymer, having one or more other monomer units.
[0092] As noted above, the reactor supply on line 101 may also include one or more modification components such as one or more induced condensation agents or ICAs. Illustrative ICAs include, but are not limited to, propane, butane, isobutane, pentane, isopentane, hexane, isomers thereof, derivatives thereof, and combinations thereof. ICAs can be introduced to provide reactor power 101 to reactor 103 having an ICA concentration ranging from a low of approximately 1 mol%, approximately 5 mol% or approximately 10 mol% to a high of approximately 25 mol%, approximately 35 mol% or approximately 45 mol%. Typical concentrations of ICAs can range from approximately 10 mol%, approximately 12 mol% or approximately 14 mol% to an increase of approximately 16 mol%, approximately 18 mol%, approximately 20 mol%, approximately 22 mol% or approximately 24 mol% . Reactor 101 supplies may include other non-reactive gases such as nitrogen and / or argon. Additional details regarding ICAs are described in U.S. Patent Nos. 5,352,749; 5,405,922; 5,436,304; and 7,122,607; and WO Publication No. 2005/113615 (A2). Condensation mode operation, as described in U.S. Patent Nos. 4,543,399 and 4,588,790 can also be used to assist in the removal of heat from the polymerization reactor 103.
[0093] The catalyst feed on line 102 can include any catalyst or combination of catalysts. Illustrative catalysts may include, but are not limited to, Ziegler-Natta catalysts, chromium based catalysts, metallocene catalysts and other single site catalysts including Group 15 containing catalysts, bimetallic catalysts and various catalysts. The catalyst can also include AlCl3, cobalt, iron, palladium, chromium / chromium oxide or "Phillips" catalysts. Any catalyst can be used alone or in combination with any other catalyst.
Suitable metallocene catalyst compounds may include, but are not limited to, the metallocenes described in U.S. Patent Nos .: 7,179,876; 7,169,864; 7,157,531; 7,129,302; 6,995,109; 6,958,306; 6.884748; 6,689,847; 5,026,798; 5,703,187; 5,747,406; 6,069,213; 7,244,795; 7,579,415; U.S. Patent Application Publication No. 2007/0055028; and WO 97/22635 Publications; WO 00/699/22; WO 01/30860; WO 01/30861; WO 02/46246; WO 02/50088; WO 04/022230; WO 04/026921; and WO 06/019494.
[0095] The "Group 15 containing catalyst" can include metal complexes from Group 3 to Group 12, where the metal has a coordination number from 2 to 8, the coordinating portion or portions including at least two atoms from Group 15 and up to four atoms in Group 15. For example, the Group 15 containing catalyst component may be a complex of a Group 4 metal and one to four linkers such that the Group 4 metal has at least coordination number 2, the portion or coordination portions including at least two nitrogens. Compounds containing Representative Group 15 are described in Publication No. WO 99/01460; European Publication No. EP0893454A1; EP 0894005A1; U.S. Patent Nos. 5,318,935; 5,889,128; 6,333,389; and 6,271,325.
Illustrative Ziegler-Natta catalyst compounds are described in European Patent Nos. EP 0103120; EP 1102503; EP 0231102; EP 0703246; U.S. Patent Nos. RE 33,683; 4,115,639; 4,077,904; 4,302,565; 4,302,566; 4,482,687; 4,564,605; 4,721,763; 4,879,359; 4,960,741; 5,518,973; 5,525,678; 5,288,933; 5,290,745; 5,093,415; and 6,562,905; and U.S. Patent Application Publication No. 2008/0194780. Examples of such catalysts include those comprising Group 4, 5, or 6 transition metal oxides, alkoxides and halides, or titanium, zirconium or vanadium halide oxides and compounds; optionally in combination with a magnesium compound, internal and / or external electron donors (alcohols, ethers, siloxanes, etc.), alkyl aluminum or boron and alkyl halides and inorganic oxide supports.
[0097] Suitable chromium catalysts can include disubstituted chromates, such as CrO2 (OR) 2; where R is triphenylsilane or a tertiary polyalicyclic alkyl. The chromium catalyst system can further include CrO3, chromocene, silyl chromate, chromyl chloride (CrO2Cl2), chromium 2-ethylhexanoate or chromium acetylacetonate (Cr (AcAc) 3). Other non-limiting examples of chromium catalysts are described in U.S. Patent No. 6,989,344 and WO2004 / 060923.
[0098] The varied catalyst can be a bimetallic catalyst composition or a multicatalyst composition. As used in this application, the terms "bimetallic catalyst composition" and "bimetallic catalyst" include any composition, mixture or system that includes two or more different catalyst components, each having a different metal group. The terms "multicatalyst composition" and "multicatalyst" include any composition, mixture or system that includes two or more different catalyst components despite the metals. Therefore, the terms "bimetallic catalyst composition", "bimetallic catalyst", "multicatalyst composition" and "multicatalyst" will be collectively referred to in this application as a "varied catalyst" unless specifically noted otherwise. In one example, the varied catalyst includes at least one metallocene catalyst component and at least one non-metallocene component.
[0099] In some embodiments, an activator can be used with the catalyst compound. As used in this application, the term "activator" refers to any compound or combination of compounds, supported or unsupported, that can activate a catalyst component or component, such as creating a cationic species of the catalyst component. Illustrative activators include, but are not limited to aluminoxane (for example, methylaluminoxane "MAO"), modified aluminoxane (for example, modified methylaluminoxane "MMAO" and / or tetraisobutyldialuminoxane "TIBAO"), and alkylaluminium compounds, ionizing activators (neutral or ionic) such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron can also be used, and combinations thereof.
[0100] The catalyst compositions can include a carrier material or vehicle. As used in this application, the terms "support" and "vehicle" are used interchangeably and are any support material, including a porous support material, for example, talc, inorganic oxides and inorganic chlorides. The catalyst component (s) and / or activator (s) may be deposited, contacted, vaporized, linked or incorporated, adsorbed or absorbed within or on one or more supports or vehicles. Other support materials may include resinous support materials such as polystyrene, functionalized or interconnected organic supports, such as divinyl benzene polystyrene polystyrene or polymeric compounds, zeolites, clays, or any other organic or inorganic support material or mixtures thereof.
[0101] Suitable catalyst supports are described in U.S. Patent Nos .: 4,701,432. 4,808,561; 4,912,075; 4,925,821; 4,937,217; 5,008,228; 5,238,892; 5,240,894; 5,332,706; 5,346,925; 5,422,325; 5,466,649; 5,466,766; 5,468,702; 5,529,965; 5,554,704; 5,629,253; 5,639,835; 5,625,015; 5,643,847; 5,665,665; 5,698,487; 5,714,424; 5,723,400; 5,723,402; 5,731,261; 5,759,940; 5,767,032; 5,770,664; and 5,972,510; and WO Nos. WO 95/32995; WO 95/14044; WO 96/06187; WO 97/02297; WO 99/47598; WO 99/48605; and WO 99/50311.
[0102] The cycle fluid through line 515 can be pressurized or compressed at pump 570 and then introduced into heat exchanger 575 where heat can be exchanged between the cycle fluid and a heat transfer medium. For example, during normal operating conditions, a cool or cold heat transfer medium via line 571 can be introduced into heat exchanger 575 where heat can be transferred from the cycle fluid in line 515 to produce a heat transfer medium. heat heated through line 577 and a cooled cycle fluid through line 515. The terms "fresh heat transfer medium" and "cold heat transfer medium" refer to a heat transfer medium having a lower temperature than fluidized bed 512 within reactor 103. Illustrative heat transfer media may include, but are not limited to, water, air, glycol or the like. It is also possible to locate the compressor 570 downstream from the heat exchanger 575 or at an intermediate point between several heat exchangers 575.
[0103] After cooling, all or a portion of the cycle fluid in line 515, the cycle fluid can be returned to reactor 103. The cycle fluid cooled in line 515 can absorb the reaction heat generated by the polymerization reaction. The 575 heat exchanger can be of any type of heat exchanger. Illustrative heat exchangers may include, but are not limited to, hull-tube, plate and frame, U-tube, and the like. For example, the heat exchanger 575 can be a shell-tube heat exchanger where the cycle fluid through line 515 can be introduced on the tube side and the heat transfer medium can be introduced on the shell side of the heat exchanger. heat 575. If desired, two or more heat exchangers can be employed, in series, parallel or combination of series and parallel, to reduce or increase the temperature of the cycle fluid in stages.
[0104] Preferably, the cycle gas through line 515 is returned to reactor 103 and fluidized bed 512 by a fluid distribution plate ("plate") 519. Plate 519 can prevent polymer particles from settling and clumping in a solid mass. Plate 519 can also prevent or reduce the accumulation of liquid at the bottom of reactor 103. Plate 519 can also facilitate transitions between processes containing liquid in cycle current 515 and those that do not and vice versa. Although not shown, the cycle gas through line 515 can be introduced into reactor 103 by a deflector disposed or located intermediate at one end of the reactor 103 and the distribution plate 519. Illustrative baffles and distribution plates suitable for this purpose are described in the patents US Nos. 4,877,587; 4,933,149; and 6,627,713.
[0105] The catalyst feed through line 102 can be introduced into fluidized bed 512 inside reactor 103 by one or more injection nozzles (not shown) in the fluid transmission with line 102. The catalyst feed is preferably introduced as preformed particles in one or more liquid vehicles (ie a catalyst slurry). Suitable liquid vehicles may include mineral oil and / or liquid or gaseous hydrocarbons including, but not limited to, butane, pentane, hexane, heptane, octane, isomers thereof or mixtures thereof. A gas that is inert to the catalyst slurry such as, for example, nitrogen or argon can also be used to transport the catalyst slurry in reactor 103. In one example, the catalyst can be a dry powder. In another example, the catalyst can be dissolved in a liquid vehicle and introduced into reactor 103 as a solution. The catalyst through line 102 can be introduced into reactor 103 at a rate sufficient to maintain the polymerization of the monomer (s) therein. The polymeric product via line 104 can be discharged from reactor 103 by operational flow control devices 109, 110, and 111. The polymeric product via line 104 can be introduced into a plurality of purge compartments or separation units, in series, parallel, or combination of series and parallel, to further separate gases and / or liquids from the product. The particular timing sequence of flow control devices 109, 110, 111 can be accomplished by using conventional programmable controllers that are well known in the art. Other suitable product discharge systems are described in U.S. Patent No. 6,548,610; U.S. Patent Application Publication No. 2010/014305; and PCT Publications WO2008 / 045173 and WO2008 / 045172.
[0106] Reactor 103 can be equipped with one or more discharge lines 518 to allow bed discharge during startup, operation and / or shutdown. Reactor 103 can be free from the use of wall agitation and / or scraping. The cycle line 515 and the elements in it (compressor 570, heat exchanger 575) may have a smooth surface and free from unnecessary obstructions to prevent the flow of cycle fluid or captured particles.
[0107] Polymerization conditions vary depending on monomers, catalysts, catalyst systems and equipment availability. The specific conditions are known or readily derivable by those skilled in the art. For example, temperatures can be within the range of approximately -10 ° C to approximately 140 ° C, often approximately 15 ° C to approximately 120 ° C, and more often approximately 70 ° C to approximately 110 ° C. The pressures can be within the range of approximately 10 kPag to approximately 10,000 kPag, such as approximately 500 kPag to approximately 5,000 kPag or approximately 1,000 kPag to approximately 2,200 kPag, for example, further polymerization details can be found in US Patent No. 6,627. 713.
[0108] In some embodiments, one or more continuity additives or static control agents can also be introduced into reactor 103 to prevent agglomeration. As used in this application, the term "continuity additive" refers to a compound or composition that when introduced into a reactor 103 can influence or direct the static charge (negatively, positively or at zero) in the fluidized bed. The introduction of continuity additive (s) may include the addition of negative charge generation chemicals to balance positive voltages or the addition of positive charge generation chemicals to neutralize negative voltage potentials. Antistatic substances can also be added to prevent or neutralize the generation of electrostatic charge continuously or intermittently. The continuity additive, if used, can be introduced with the reactor feed through line 101, the catalyst feed through line 102, a separate inlet (not shown), or any combination thereof. The particular continuity additive or combination of continuity additives may depend, at least in part, on the nature of the static charge, the particular polymer that is produced within the polymerization reactor, the particular dry spray catalyst system or the combination of catalyst systems that are used or a combination thereof. Suitable continuity additives are described in European Patent 0229368; U.S. Patent Nos. 5,283,278; 4,803,251; 4,555,370; 4,994,534; and 5,200,477; and Publication WO No. WO2009 / 023111; and WO01 / 44322.
[0109] The use of the cooling / "self-cooling" system 160 described in this application can act on several common problems with gaseous polyolefin purge systems, since it allows high nitrogen demand for resin purification, reduces or eliminates ethylene losses in process discharges, and reduces or eliminates reactive gases that cause clogging in the discharge recovery system and clogging in general. The recovery system 160 described in this application is also capable of processing a wide range of opening compositions.
[0110] The process described in this order allows condensation before on the compression train. This results in a reduced concentration of activators, such as triethyl aluminum alkyls (TEAL), in the gas due to absorption in condensed liquids. It is believed that the presence of activators / cocatalysts causes the discharge recovery compressor to clog over time, so it is beneficial to have reduced concentrations in the compression train.
[0111] The system described in this application can use atypical compression ratios, in which the compression ratio is increased from the first stage to the third stage of the compressor. High proportions of compression can lead to higher compressor discharge temperatures and higher pressures can lead to higher partial monomer pressure. Higher monomer partial pressure and higher temperatures can result in more reactive conditions. By using a lower compression ratio in the higher pressure stages (ie, the first stage), the system described in this order reduces the potential for clogging. Examples
[0112] To provide a better understanding of the preceding discussion, the following non-limiting examples are provided. Although the examples are directed to specific modalities, they should not be considered as a limitation of the invention in any specific respect. All parts, proportions and percentages are by weight unless otherwise indicated. Three simulated examples were prepared (example 1-3). The particular polymerization conditions used to produce the simulated results are shown in Table 1. The polymerization system for producing polymer products and recovering volatiles from it was simulated using the polymerization system 100 discussed and described above with reference to Figure 1, according with one or more modalities. The computer simulation program ASPEN PLUS® from Aspen Technology, Inc. was used to generate the data for the three examples (example 1-3). The simulations assume steady-state modeling, instead of transient conditions such as starting the equipment. The compressor capacity is also calculated to be compatible with the minimum stable requirement of each simulation, as such without recycling the compressed purge gas product to the compressor (s) inlet is included. Heat exchangers 118, 130, 137, and 145 are assumed to each cool the stream of gaseous product from the purge to 35 ° C.

[0113] The first simulated example (example 1) assesses the separation of a gaseous product from the purge recovered from a low density linear ethylene / butene copolymer that has a melt index (I2) of 1.0 and a density of 0.918 g / cm3. The second simulated example (example 2) assesses the separation of a gaseous product from the purge recovered from a low density linear ethylene / hexene copolymer that has a melt index (I2) of 1.0 and a density of 0.918 g / cm3. The third simulated example (example 3) evaluates the polymerization of a high density linear polyethylene homopolymer having a melt index (I2) of approximately 8.2 and a density of approximately 0.963 g / cm3. As shown in the tables below, the flow rate of the gaseous product from the purge through line 116 recovered from the purge compartment 115 ranges from approximately 5,558 kg / h for Example 1 below to approximately 2,664 kg / h for example 3.
[0114] The results of the three simulations of Examples 1-3 are shown in Tables 2A-C, 3A-C and 4A-C, respectively. The current numbers correspond to those discussed and described above with reference to Figure 1.



[0115] The simulated data shown in Tables 2A-C in which the polymerization of the ethylene / butene copolymer is produced shows that the purge gas introduced through line 122 to the compression system 125 contains approximately 30% by weight of nitrogen, 11 % by weight of ethylene (monomer), approximately 5% by weight of ethane, approximately 20% by weight of butene (comonomer), approximately 3% by weight of C4 aggregates and approximately 26% by weight of isopentane (ICA) and has a normal flow rate of approximately 4,636 kg / h, which includes the third product recovered from the multistage cooler 161 and recycled through line 186 to the purge gas in line 116.
[0116] The maximum temperature that the gaseous purge product reaches during the purge gas separation is 124.1 ° C as the purge gaseous product compressed through line 143 comes out of the third compressor 142. The pressure ratio at which the first compressor 128 compresses the gaseous product of the purge is greater than the second and third compressors 135, 142. More particularly, the compressed gaseous product recovered through line 129 of the first compressor 128 is compressed in a pressure ratio of 1: 3 61, the compressed purge gas product recovered through line 136 of the second compressor is compressed in a pressure ratio of 1: 3.23, and the compressed purge gas product recovered through line 143 of the third compressor 142 is compressed in a pressure ratio of 1: 3.36. In addition, heat exchangers 118, 130, and 137 cool the gaseous purging product and the compressed gaseous purging products introduced into it via lines 116, 129, and 136 at a temperature of 34.5 ° C, 19.4 ° C, and 35 ° C, respectively, further reducing the temperature rise caused by compression.
[0117] The compressed purge gas recovered through line 149 of the compression system 125 is at a pressure of approximately 42.07 kg / cm2a (approximately 4,130 kPa) and a temperature of approximately 35 ° C. The cooled purge gas recovered through line 162 of the multistage heat exchanger 161 is separated into the gas / liquid separator 163 to produce the gaseous product through line 164 and the condensed product through line 165 at a temperature of approximately -69 ° C. Additional expansion and / or separation of the gaseous product through line 164 and the condensed product through line 165 produces three chilled products, ie the first product through line 173, the second product through line 177 and the third product through line 184 at temperatures of -71 ° C, -69 ° C, and -94.6 ° C, respectively.
[0118] Also shown in Tables 2A-C, the compression and self-cooling systems 125, 160 provide sufficient separation of various components of the gaseous purging product, that is, nitrogen (purging gas), ethylene (monomer) and isopentene / butene (ICA / comonomer) such that the separate components can be recycled within the polymerization system 100 in the appropriate positions instead of having to be discharged, burned, consumed as fuel, or otherwise removed from the polymerization system. For example, the first product through line 174 is high enough in light components, including in this case nitrogen at 88% by weight and low enough in heavy components (for example, butene at <0.005% by weight and isopentane at <0.005% by weight) that the first product can be used as the purge gas through line 112 to purge the polymeric product. In another example, the second product through line 178 is sufficiently high in light hydrocarbons (ethylene at approximately 28.8% by weight, ethane at approximately 15.1% by weight and 28.4% by weight of butene) than the second product through line 178 can be recycled back to the polymerization reactor 103, thereby recycling the monomer (ethylene) and comonomer (butene) to it. In addition, since the second product through line 178 is at a pressure of approximately 2,760 kPa, the second product through line 178 can be recycled directly to the polymerization reactor 103 which is operated at a pressure of approximately 2,377 kPa without further compression . In another example, the third product in line 185 contains approximately 31.1% by weight of ethylene, approximately 15.9% by weight of ethane and approximately 26.3% by weight of butene. As such, at least a portion of the third product on line 185 can be recycled via line 186 to the gaseous purging product on line 116, which can increase the concentration of the lightest components, for example, ethylene and ethane, in the gaseous product of purge compressed on line 149 to maintain a desired level of refrigerant within the self-cooling system 160.



[0119] The simulated data shown in Tables 3A-C in which the polymerization of the ethylene / hexene copolymer is produced shows that the gaseous purging product introduced through line 122 to the compression system 125 contains approximately 38.4% by weight of nitrogen , 10.6% by weight of ethylene (monomer), approximately 5.7% by weight of ethane, approximately 18.5% by weight of hexene (comonomer) and approximately 24.7% by weight inert C6 and has a rate of normal flow of approximately 5,929 kg / h, which includes the third product recovered from the multistage cooler 161 and recycled through line 186 to the purge gas on line 116.
[0120] The maximum temperature that the gaseous purge product reaches during the purge gas separation is 151.6 ° C as the purge gas compressed through line 143 exits the third compressor 142. The pressure ratio at which the first compressor 128 compresses the gaseous product of the purge is greater than the second and third compressors 135, 142. More specifically, the simulated example conditions used the same pressure ratios of the compressors 128, 135, 142 as in example 1, which are 1: 3.61, 1: 3.23, and 1: 3.36, respectively. In addition, heat exchangers 118, 130, and 137 cool the gaseous purging product and the compressed gaseous purging products introduced there through lines 116, 129, and 136 at a temperature of 34.6 ° C, 34.8 ° C and 35.0 ° C, respectively, further reducing the temperature rise caused by compression.
[0121] The compressed purge gas recovered through line 149 of the compression system 125 is at a pressure of approximately 42.07 kg / cm2a (approximately 4,130 kPa) and a temperature of approximately 35 ° C. The cooled purge gas recovered through line 162 of the multistage heat exchanger 161 is separated into the gas / liquid separator 163 to produce the gaseous product through line 164 and the condensed product through line 165 at a temperature of approximately -77.2 ° C. Additional expansion and / or separation of the gaseous product through line 164 and the condensed product through line 165 produces three chilled products, ie the first product through line 173, the second product through line 177 and the third product through line 184 at temperatures of -116 ° C, -77.2 ° C and - 102.0 ° C, respectively. Also shown in Tables 3A-C, the compression and self-cooling systems 125, 160 provide sufficient separation of various components of the gaseous purging product, that is, nitrogen (purging gas), ethylene (monomer) and isopentene / butene (ICA / comonomer) such that the separate components can be recycled within the polymerization system 100 in the appropriate positions instead of having to be discharged, burned, consumed as fuel, or otherwise removed from the polymerization system. For example, the first product through line 174 is high enough in light components, including in this case, nitrogen in 90.5% by weight and low enough in heavy components (for example, butene at <0.005% by weight and isopentane at < 0.005% by weight) that the first product can be used as the purge gas through line 112 to purge the polymeric product. In another example, the second product through line 178 is high enough in light hydrocarbons (ethylene at approximately 40.7% by weight and ethane at approximately 33.9% by weight) that the second product through line 178 can be recycled back to the polymerization reactor 103, thereby recycling the monomer (ethylene) and comonomer (butene) to it. In addition, since the second product through line 178 is at a pressure of approximately 2,760 kPa, the second product through line 178 can be recycled directly to the polymerization reactor 103 which is operated at a pressure of approximately 1,894 kPa without further compression . In another example, the third product in line 185 contains approximately 42.8% ethylene by weight and approximately 34.1% by weight of ethane. As such, at least a portion of the third product on line 185 can be recycled via line 186 to the gaseous purging product on line 116, which can increase the concentration of the lighter components, for example, ethylene and ethane, in the gaseous product. of the compressed purge in line 149 to maintain a desired level of refrigerant within the self-cooling system 160.






[0122] The simulated data shown in Tables 4A-C, in which the polymerization of the ethylene homopolymer is produced, show that the purge gas introduced through line 122 to the compression system 125 contains approximately 30.5% by weight of nitrogen , 26.8% by weight of ethylene (monomer), approximately 8% by weight of ethane and approximately 31.3% by weight of isopentane and has a normal flow rate of approximately 3,092 kg / h, which includes the third product recovered from the multi-stage cooler 161 and recycled through line 186 to the purge gas on line 116.
[0123] The maximum temperature that the gaseous purge product reaches during the purge gas separation is 128.8 ° C as the gaseous purge product compressed through line 143 comes out of the third compressor 142. The pressure ratio at which the first compressor 128 compresses the gaseous product of the purge is greater than the second and third compressors 135, 142. More specifically, the simulated example conditions used the same pressure ratios of compressors 128, 135, 142 as in example 1, which are 1 : 3.61, 1: 3.23, and 1: 3.36, respectively. In addition, the heat exchangers 118, 130, and 137 cool the gaseous purging product and the compressed gaseous purging products introduced there through lines 116, 129, and 136 at a temperature of 34.3 ° C, 15.6 ° C, and 35.0 ° C, respectively, further reducing the temperature rise caused by compression.
[0124] The compressed purge gas recovered through line 149 of the compression system 125 is at a pressure of approximately 42.07 kg / cm2a (approximately 4,130 kPa) and a temperature of approximately 35 ° C. The cooled purge gas recovered through line 162 of the multistage heat exchanger 161 is separated into the gas / liquid separator 163 to produce the gaseous product through line 164 and the condensed product through line 165 at a temperature of approximately -79.2 ° C. Additional expansion and / or separation of the gaseous product through line 164 and the condensed product through line 165 produces three chilled products, that is, the first product through line 173, the second product through line 177 and the third product through line 184 at temperatures of -108.7 ° C, -79.2 ° C, and - 102.6 ° C, respectively.
[0125] Also shown in Tables 4A-C, the compression and self-cooling systems 125, 160 provide sufficient separation of various components of the gaseous purging product, that is, nitrogen (purging gas), ethylene (monomer) and isopentene / butene (ICA / comonomer) such that the separate components can be recycled within the polymerization system 100 in the appropriate positions instead of having to be discharged, burned, consumed as fuel, or otherwise removed from the polymerization system. For example, the first product through line 174 is high enough in light components, including in this case, nitrogen in approximately 83.1% by weight and low enough in heavy components (for example, butene in <0.005% by weight and isopentane in <0.005% by weight) that the first product can be used as the purge gas through line 112 to purge the polymeric product. In another example, the second product through line 178 is high enough in light hydrocarbons (ethylene at approximately 51.4% by weight and ethane at approximately 16.2% by weight) that the second product through line 178 can be recycled back to the polymerization reactor 103, thereby recycling the monomer (ethylene) and comonomer (butene) to it. In addition, since the second product through line 178 is at a pressure of approximately 2,760 kPa, the second product through line 178 can be recycled directly to the polymerization reactor 103 which is operated at a pressure of approximately 2,515 kPa without additional compression. . In another example, the third product in line 185 contains approximately 52.3% by weight of ethylene and approximately 16.3% by weight of ethane. As such, at least a portion of the third product on line 185 can be recycled via line 186 to the gaseous purging product on line 116, which can increase the concentration of the lightest components, for example, ethylene and ethane, in the gaseous product of purge compressed on line 149 to maintain a desired level of refrigerant within the self-cooling system 160.
[0126] All numerical values are "close" or "approximately" the indicated value and consider experimental error and variations that would be expected by a person having ordinary skill in the technique. All pressure values refer to absolute pressure unless otherwise indicated.
[0127] Several terms have been defined above. To the extent that a term used in a claim is not defined above, the broadest definition in the relevant technique should be given by people who gave that term as reflected in at least one printed publication or issued patent. In addition, all patents, testing procedures and other documents cited in this patent application are fully incorporated to the extent that such disclosure is quite consistent with this patent application and for all jurisdictions in which such incorporation is permitted.
[0128] While the foregoing is directed to modalities of the present invention, other and additional modalities of the invention can be invented without departing from its basic scope, and the scope of this is determined by the claims that follow.

权利要求:
Claims (15)
[0001]
1. Method for recovering hydrocarbons from a gaseous polyolefin purge product, characterized by the fact that it comprises: - recovering a polyolefin product comprising one or more volatile hydrocarbons from a polymerization reactor (103); - contacting the polyolefin product with a purge gas to remove at least a portion of the volatile hydrocarbons to produce a polymeric product having a reduced concentration of volatile hydrocarbons and a purified gaseous product enriched in volatile hydrocarbons, wherein the volatile hydrocarbons comprise hydrogen , methane, one or more C2-C12 hydrocarbons or any combination thereof, and the gaseous product of the purge is at a pressure of 50 KPa to 250 KPa; - compress the gaseous product of the purge at a pressure of 2,500 KPa to 10,000 KPa; the gaseous purging product being compressed in at least two stages (128, 135, 142), with the first stage (128) compressing the gaseous purging product in a product proportion that is equal to or greater than the proportion pressure of subsequent stages; - cool the gaseous product of the compressed purge; - separating the gaseous product from the cooled purge into a gaseous product including at least a first product and a condensed product including a second product and a third product; and - recycling at least a portion of at least one of the first product as a purging gas, the second product for the polymerization reactor (103) or the third product for the gaseous purging product enriched in volatile hydrocarbons prior to compression.
[0002]
2. Method according to claim 1, characterized in that the gaseous purging product is compressed in two or more stages (128, 135), the first stage (128) compressing the purging gaseous product in a proportion pressure from 1: 6 to 1:10, and the second stage (135) compresses the gaseous purging product in a pressure ratio of 1: 3 to 1: 6 ..
[0003]
Method according to either of claims 1 or 2, characterized in that the compression of the gaseous purging product comprises serial compression of the gaseous purging product in two or more compression stages (128, 135, 142), and the compressed purge gas recovered from each compression stage (128, 135, 142) being cooled and at least a portion of any condensed liquid is separated from each compressed purge gas after each compression stage (128 , 135, 142) to produce a condensed product and a compressed gas product.
[0004]
4.. Method according to claim 3, characterized in that it also comprises recycling at least a portion of one or more condensed products to the polymerization reactor (103).
[0005]
5. Method according to any one of claims 1 to 4, characterized in that the cooling of the compressed purging product comprises introducing the compressed purging product into a refrigeration system (160), wherein at least a portion of the gaseous product from the compressed purge is used as a refrigerant in the refrigeration system (160).
[0006]
6. Method according to any of claims 1 to 5, characterized in that the gaseous product of the compressed purge is at a pressure of 3,100 KPa to 4,500 KPa.
[0007]
Method according to any one of claims 1 to 6, characterized in that the gaseous product of the compressed purge is cooled to a temperature below -65 ° C.
[0008]
Method according to any one of claims 1 to 7, characterized in that the temperature of the purge gas product is maintained at a temperature below 200 ° C during compression.
[0009]
Method according to any one of claims 1 to 8, characterized in that the first product comprises less than 500 ppm by volume of C4 hydrocarbons, less than 250 ppm by volume of C5 hydrocarbons, less than 100 ppm by volume of C6 hydrocarbons, and less than 100 ppm by volume of C7 hydrocarbons and heavier hydrocarbons.
[0010]
10. System for the recovery of hydrocarbons from a gaseous polyolefin purge product, for carrying out the method defined in claim 1, characterized in that it comprises: - a purge compartment (115) adapted to receive a polyolefin product comprising one or more volatile hydrocarbons from a polymerization reactor (103), wherein the polyolefin product is contacted with a purge gas inside the purge compartment (115) to remove at least a portion of the volatile hydrocarbons to produce a polyolefin product having a concentration reduced amount of volatile hydrocarbons and a gaseous purging product enriched in volatile hydrocarbons, where the volatile hydrocarbons comprise hydrogen, methane, one or more C2-C12 hydrocarbons or any combination thereof, and where the gaseous purging product is at a pressure from 50 KPa to 250 KPa; - a compression system (125) having at least two compressors (128, 135, 142) adapted to compress the gaseous product of the purge at a pressure of 2,500 KPa a and 10,000 KPa; the gaseous purging product being compressed in a first stage (128) at a pressure ratio that is equal to or greater than the pressure ratio of subsequent stages; - a cooling system (160) adapted to cool and separate the gaseous product from the compressed purge into a gaseous product, including a first product, and a condensed product including a second product, and a third product; and - at least one recycling line (144, 205, 305, 310, 315) adapted to recycle at least a portion of at least one of the first product as the purge gas, the second product for the polymerization reactor (103) , and the third product to the gaseous purging product enriched in volatile hydrocarbons before compression.
[0011]
System according to claim 10, characterized in that it further comprises a recycling line (144) adapted to recycle at least a portion of the compressed purging gaseous product to the purging gaseous product before compression.
[0012]
System according to either of claims 10 or 11, characterized in that the compression system (125) further comprises at least one recycling line adapted (210, 215, 305, 310, 315) for recycling a portion of the compressed purge gas after compression in at least one of the compressors upstream of the compressor (128, 135, 142).
[0013]
13. System according to any one of claims 10 to 12, characterized in that the compression system (125) comprises two or more compressors (128, 135, 142), one or more heat exchangers (130, 137, 145) adapted to cool the compressed purge gas recovered from each compressor (128, 135, 142), and one or more separators (132, 139, 147) adapted to separate at least a portion of any condensed fluid from of the compressed purge gas product after each compressor (128, 135, 142).
[0014]
14. System according to any one of claims 10 to 13, characterized in that the cooling system (160) comprises one or more heat exchangers (161) adapted to cool the compressed purge gas by indirectly exchanging the heat of the compressed purge gas to three or more products produced within the refrigeration system (160), and each of the three or more products comprises a portion of the compressed purge gas after cooling.
[0015]
15. System according to any one of claims 10 to 14, characterized in that the cooling system (160) is adapted to use the compressed purge gas product as a source of a refrigerant in the cooling system (160) .

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法律状态:
2018-05-29| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-04-07| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-10-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201061424300P| true| 2010-12-17|2010-12-17|

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US61/424,300|2010-12-17|

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PCT/US2011/064525|WO2012082674A1|2010-12-17|2011-12-13|Systems and methods for recovering hydrocarbons from a polyolefin purge gas product|

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