# US 10,501,566 B2 · Production method of alpha-olefin low polymer and production apparatus > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,501,566 B2 - Document ID: US10501566B2 - Status: Granted - Kind: B2 - Application number: 15/715,545 - Filed: 2017-09-26 - Published: 2018-02-01 - Granted: 2019-12-10 - Earliest claimed: 2015-09-28 - Assignees: Mitsubishi Chemical Corporation - Applicants: Mitsubishi Chemical Corporation - Inventors: Hiroki Emoto - Web page: https://patentgrep.com/patent/US10501566B2 ## CPC - C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers - B01D 3/14: Fractional distillation {or use of a fractionation or rectification column} - B01D 5/00: Condensation of vapours; Recovering volatile solvents by condensation (B01D8/00 takes precedence; condensers F28B) - B01D 5/0012: {Vertical tubes} - B01D 5/0057: {in combination with other processes} - B01D 5/0081: {Feeding the steam or the vapours} - C07C 2/08: Catalytic processes - C07C 2/32: as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} - C07C 11/107: with six carbon atoms - C08F 10/02: Ethene - F28D 7/16: the conduits being arranged in parallel spaced relation ({F28D7/0008 - F28D7/0058 take precedence}; F28D7/02 - F28D7/10 take precedence) - F28F 9/0265: {by using guiding means or impingement means inside the header box} - F28F 9/027: {in the form of distribution pipes} - F28G 1/16: using jets of fluid for removing debris (F28G1/12 takes precedence) - F28G 9/00: Cleaning by flushing or washing, e.g. with chemical solvents (appliances using jets of fluid for removing debris F28G1/16, F28G3/16) - C08F 2500/02: Low molecular weight, e.g. <100,000 Da. - C08F 2500/03: Narrow molecular weight distribution, i.e. Mw/Mn < 3 - C08F 2500/07: High density, i.e. > 0.95 g/cm3 - F28D 2021/0022: {for chemical reactors} - F28D 2021/0063: {Condensers} - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - F28D: HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT (fluid heaters having heat generating means and heat transferring means F24H; furnaces F27; details of heat-exchange apparatus of general) - F28F: DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION (water and air traps, air venting F16) - F28G: CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS (cleaning pipes or tubes in general B08B9/02; devices or arrangements for removing water, minerals, or sludge from boilers while the boiler is in operation, or which remain in position while the boiler is in operation, or are specifically adapted to boilers without any other utility F22B37/48; removal or treatment of combustion products or combustion residues F23J; removing ice from heat-exchange apparatus F28F17/00) ## Abstract The present invention relates to a method and an apparatus for producing an α-olefin low polymer by subjecting an α-olefin to low polymerization reaction in the presence of a catalyst in a liquid phase part within a reactor, and the present invention relates to a method and an apparatus for producing an α-olefin low polymer, such as 1-hexene, etc., by subjecting an α-olefin, such as ethylene, etc., to low polymerization reaction, in which the formation of a polymer on an upper tube plate surface of a shell and tube type heat exchanger that is used for heat removal is suppressed, thereby performing a continuous operation stably over a long period of time. ## Claims ### Claim 1 A method for oligomerizing at least one α-olefin and concurrently spraying atomized droplets in a shell and tube heat exchanger that is operatively coupled with the oligomerizing, the method comprising: oligomerizing the α-olefin in an oligomerization reactor in the presence of a catalyst to produce at least one α-olefin oligomer, wherein the reactor comprises a gas phase and a liquid phase; withdrawing a portion of the gas from the gas phase of the oligomerization reactor; introducing the withdrawn gas through a gas supply port into the shell and tube heat exchanger, wherein the introduced gas has a density of 20 kg/m3 or more, and the gas flow rate of the introduced gas from the gas supply port is 1 m/s or more; cooling the introduced gas in the shell and tube heat exchanger to obtain a condensed liquid; recycling a portion of the condensed liquid into the reactor; and supplying into the shell and tube heat exchanger atomized droplets of a portion of the condensed liquid, of a liquefied α-olefin, and/or of a circulation solvent from the bottom of a downstream separation column, wherein: the shell and tube heat exchanger comprises jet nozzles for supplying the atomized droplets between the gas supply port and a tube plate disposed in a horizontally opposite direction to the gas supply port in the shell and tube heat exchanger; five or more of the jet nozzles are provided per 1.00 m2 of an area of the tube plate; and the jet nozzles include at least one nozzle that is inclined toward the gas supply port from the horizontal direction. ### Claim 2 (depends on 1) The method according to claim 1, wherein the atomized droplets comprise the condensed liquid. ### Claim 3 (depends on 1) The method according to claim 1, wherein a Sauter mean diameter of the atomized droplets is 3 mm or less. ### Claim 4 (depends on 1) The method according to claim 1, wherein the jet nozzles comprise a spray nozzle. ### Claim 5 (depends on 1) The method according to claim 1, wherein the α-olefin is ethylene. ### Claim 6 (depends on 1) The method according to claim 1, wherein the jet nozzles comprise a full cone spray nozzle. ### Claim 7 (depends on 6) The method according to claim 6, wherein a spray angle of the full cone spray nozzle is 15° to 170°. ### Claim 8 (depends on 1) The method according to claim 1, wherein the jet nozzles also include at least one radially obliquely upward nozzle, in which radially obliquely upward is relative to an axis of the tube plate. ### Claim 9 (depends on 1) The method according to claim 1, wherein the jet nozzles include at least one vertically downward central nozzle and at least one radially obliquely downward nozzle, in which vertically downward and radially obliquely downward are relative to an axis of the tube plate. ### Claim 10 (depends on 1) The apparatus according to claim 1, wherein the jet nozzles protrude from the top cover of the heat exchanger. ### Claim 11 A method for oligomerizing at least one α-olefin and concurrently spraying atomized droplets in a heat exchanger that is operatively coupled with the oligomerizing, the method comprising: oligomerizing the α-olefin in an oligomerization reactor in the presence of a catalyst to produce at least one α-olefin oligomer, wherein the reactor comprises a gas phase and a liquid phase; withdrawing a portion of the gas from the gas phase of the oligomerization reactor; introducing the withdrawn gas through a gas supply nozzle into the heat exchanger, wherein the introduced gas has a density of 20 kg/m3 or more, and the gas flow rate of the introduced gas from the gas supply port is 1 m/s or more; cooling the introduced gas in the heat exchanger to obtain a condensed liquid; recycling a portion of the condensed liquid into the reactor; and supplying into the heat exchanger atomized droplets of a portion of the condensed liquid, of a liquefied α-olefin, and/or of a circulation solvent from the bottom of a downstream separation column, wherein: i) the heat exchanger comprises: a cylindrical shell; an upper tube plate and a lower tube plate disposed on an upper end side and a lower end side of the shell, respectively; a plurality of tubes installed between the upper tube plate and the lower tube plate; a top cover disposed on the upper side of the upper tube plate wherein the gas supply nozzle is provided in the top cover; a bottom cover disposed on the lower side of the lower tube plate; and a takeout port provided in the bottom of the bottom cover for removing the condensed liquid; ii) the heat exchanger comprises jet nozzles for supplying the atomized droplets between the gas supply port and the upper tube plate; iii) five or more jet nozzles are provided per 1.00 m2 of a surface area of the upper tube plate; and iv) the jet nozzles include at least one nozzle that is inclined toward the gas supply nozzle from the horizontal direction. ### Claim 12 (depends on 11) The method according to claim 11, wherein the jet nozzles also include at least one radially obliquely upward nozzle, in which radially obliquely upward is relative to an axis of the upper tube plate. ### Claim 13 (depends on 11) The method according to claim 11, wherein the jet nozzles include at least one vertically downward central nozzle and at least one radially obliquely downward nozzle, in which vertically downward and radially obliquely downward are relative to an axis of the upper tube plate. ### Claim 14 (depends on 11) The apparatus according to claim 11, wherein the jet nozzles protrude from the top cover of the heat exchanger. ### Claim 15 An apparatus, comprising: an oligomerization reactor in which a catalyst and at least one α-olefin are supplied to oligomerize the α-olefin wherein the oligomerization reactor comprises a gas phase and a liquid phase; a piping connected to the gas phase of the reactor on one end; a shell and tube heat exchanger comprising a gas supply nozzle that is connected to the other end of the piping wherein a gas withdrawn from the gas phase from the reactor is cooled in the shell and tube heat exchanger to obtain a condensed liquid; and a takeout port piping connecting the heat exchanger and the reactor for recycling of the condensed liquid into the oligomerization reactor, wherein: i) the heat exchanger further comprises: a cylindrical shell; an upper tube plate and a lower tube plate disposed on an upper end side and a lower end side of the shell, respectively; a plurality of tubes installed between the upper tube plate and the lower tube plate; a top cover disposed on the upper side of the upper tube plate wherein the gas supply nozzle is provided in the top cover; and a bottom cover disposed on the lower side of the lower tube plate wherein the takeout port is provided in the bottom of the bottom cover; ii) the gas supply nozzle is adapted to function such that the gas is introduced into the heat exchanger at a density of 20 kg/m3 or more and at a gas flow rate of 1 m/s or more; iii) the top cover further comprises jet nozzles for supplying atomized droplets onto the surface of the upper tube plate; iv) five or more of the jet nozzles are provided per 1.00 m2 of an area of the upper tube plate; and v) the jet nozzles include at least one nozzle that is inclined toward the gas supply nozzle from the horizontal direction. ### Claim 16 (depends on 15) The apparatus according to claim 15, wherein the jet nozzles comprise a spray nozzle. ### Claim 17 (depends on 15) The apparatus according to claim 15, wherein: the jet nozzles protrude from the top cover; and a direction of the atomized droplets supplied from the jet nozzles is inclined relative to a direction of the gas introduced from the gas supply nozzle from the horizontal direction. ### Claim 18 (depends on 15) The apparatus according to claim 15, wherein the jet nozzles comprise a full cone spray nozzle. ### Claim 19 (depends on 18) The apparatus according to claim 18, wherein a spray angle of the full cone spray nozzle is 15° to 170°. ### Claim 20 (depends on 15) The apparatus according to claim 15, wherein the jet nozzles also include at least one radially obliquely upward nozzle, in which radially obliquely upward is relative to an axis of the upper tube plate. ### Claim 21 (depends on 15) The apparatus according to claim 15, wherein the jet nozzles include at least one vertically downward central nozzle and at least one radially obliquely downward nozzle, in which vertically downward and radially obliquely downward are relative to an axis of the upper tube plate. ### Claim 22 (depends on 15) The apparatus according to claim 15, wherein the jet nozzles protrude from the top cover of the heat exchanger.