US3675435A - Low pressure ethylene recovery process - Google Patents

Low pressure ethylene recovery process Download PDF

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US3675435A
US3675435A US874842A US3675435DA US3675435A US 3675435 A US3675435 A US 3675435A US 874842 A US874842 A US 874842A US 3675435D A US3675435D A US 3675435DA US 3675435 A US3675435 A US 3675435A
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methane
vapor
feed
overhead
process according
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Steven B Jackson
Ernest Freireich
James D Hammond
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Fluor Corp
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Fluor Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/09—Purification; Separation; Use of additives by fractional condensation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0238—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 2 carbon atoms or more
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/04—Processes or apparatus using separation by rectification in a dual pressure main column system
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/76—Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/12—Refinery or petrochemical off-gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/02—Internal refrigeration with liquid vaporising loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • F25J2270/06—Internal refrigeration with work-producing gas expansion loop with multiple gas expansion loops
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/40—Vertical layout or arrangement of cold equipments within in the cold box, e.g. columns, condensers, heat exchangers etc.
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • Methane is separated overhead from the feed in a separation zone at a first lower pressure; a first portion of this overhead vapor is expanded through an expansion motor producing an energy output, a second portion of the overhead vapor is compresed to a second presure greater than the first pressure in a compressor driven by the motor output. The compresed vapor portion is then cooled to condense the major portion of the methane and the condensed methane is returned to the separation zone as reflux and recovering ethylene as bottoms from the separation zone. The methane vapor is recovered as fuel gas.
  • This invention is concerned with the processing of cracked gases derived from hydrocarbon feedstocks and specifically with processing operations having as their ultimate objective the economical recovery of maximum quantities of ethylene from such feedstocks.
  • the present invention provides a process adapted to the recovery of ethylene from ethylenecontaining feed gases which typically contain as well as hydrogen, appreciable quantities of methane and various heavier ends such as ethane, propane and propylene.
  • ethylenecontaining feed gases typically contain as well as hydrogen, appreciable quantities of methane and various heavier ends such as ethane, propane and propylene.
  • Particularly significant in the present development is the effective separation of methane from the ethylene at relatively low pressures and at moderate refrigeration temperatures whereby much high pressure equipment is obviated and/or expensive methane refrigeration plant requirements are avoided.
  • Prior Art Recovery of ethylene from ethylene-containing gases is widely practiced in industry. Most operations have as their central facility a demethanizer column from which methane is passed overhead and ethylene is taken as bottoms. Typical operating conditions include 450 psia pressure in the column and accumulator temperatures of about l40F. This combination keeps ethylene loss low lpercent) but is disadvantageous in that the high pressure in the demethanizer results in a greater than necessary total compressor energy requirement for refrigeration and raw gas compressors. Increased demethanizer pressure is even counterproductive as methane/ethylene separation is relatively more difficult at increased pressures.
  • Some ethylene recovery plants have so-called low pressure demethanizers. These, however, have been combined with expensive methane refrigeration cycles to produce a sufficiently low temperature for minimizing ethylene losses with the separated methane, so that the pressure-temperature problem referred to above is shifted but not resolved.
  • the invention provides a process for the removal of methane from a hydrocarbon feed containing ethylene, hydrogen, methane and higher boiling hydrocarbon components with low loss of ethylene.
  • the process includes effecting in a methane separation zone at a first pressure between about 200 and 350 psia.
  • a separation overhead of methanerich vapor which may contain up to 4 percent hydrogen and less than 2 percent ethylene by volume, expanding a first portion of the overhead vapor through an expansion motor producing an energy output from the vapor expansion, compressing a second portion of the overhead vapor to a second pressure greater than the first pressure in a compressor driven by the energy output of the motor, cooling the compressed overhead vapor portion sufficiently to condense the major portion of the methane therein, separating methane vapor from the condensed methane, returning the condensed methane to the methane separation zone as reflux and recovering ethylene and heavier components of the feed as bottoms from the methane separation zone.
  • the first vapor portion generally will comprise not less than 50 percent by volume of the methane separation zone overhead and the second overhead vapor portion accordingly will be less than 50 percent by volume of the methane separation zone overhead vapors.
  • the expansion of the first overhead vapor portion is carried out to produce an energy output which will effect the desired compression of the second overhead vapor portion.
  • the overhead first vapor portion is expanded to a pressure less than I00 psia while the second portion of the overhead vapor is compressed to a pressure above about 450 psia.
  • the first vapor portion is centrifugally expanded through a turbine type expansion motor.
  • the process further includes flashing hydrogen and methane from the hydrocarbon feed in advance of the methane separation zone and heat exchanging the flash vapor and flash liquid with incoming feed to cool the feed before flashing hydrogen and methane therefrom.
  • heat exchanging the expanded overhead vapor portion with the feed to cool the feed further prior to said flashing may also be accomplished in the process.
  • the second vapor portion may be compressed to a pressure above about 450 psia and thereafter be cooled by external refrigeration to a temperature below about l3SF, to efiect liquefaction of from 50 to percent of the methane content in the portion.
  • FIGURE schematic flow sheet illustrates one embodiment of the present invention.
  • the feed enters along line I at a temperature generally of -40 to +60F and at pressures typically between 235 and 550 psia for example 420 psia.
  • the cold process streams available from subsequent operations, to be described, are used to advantage to cool the feed, prior to fractionation of the feed, to temperatures at which hydrogen and methane may be flashed from the feed e.g. I20F to l40F.
  • Feed from line I is split to send a first portion to heat exchanger 2 along line 3. In passage along line 3, this first portion of the feed is heat exchanged in heat exchanger 4 with the product recovery stream in line 53 prior to passing the product stream to subsequent processing equipment, e.g. a deethanizer (not shown).
  • the first portion of the feed may also be cooled with auxiliary cooling means such as propylene refrigeration in heat exchanger 5, ethylene refrigeration in heat exchanger 6 as required to achieve the desired temperature in the feed.
  • the second portion of the feed controlled by valve 7 bypasses heat exchangers 4, 5 and 6 and passes along line 8 to heat exchanger 9 where this feed portion is cooled by heat exchange with exiting hydrogen-rich and methane-rich gas streams in lines 10 and 11 respectively.
  • the off-gas cooled, second feed portion is returned along line 12 to line 3 for recombination with the cooled feed first portion at 13.
  • the feed passes to a gas-liquid separator 14 having level control valve Ma, so that the feed enters separator M at approximately 120F.
  • gas and liquid phases are flash separated at a pressure of approximately 405 psia.
  • the flash liquid from this phase separation is taken as bottoms from separator 14 along line 15 and forms the main feed to the demethanizing zone, after reheating to optimum temperature in heat exchanger 2, as will be described.
  • the flash vapor from separator l4 is taken overhead in line 16 and cooled drastically in heat exchanger 17 eg. to 2l0F at 400 psia by heat exchange therein with very cold methane gas and liquid erg.
  • the flash liquid from the second flash in separator 19 is passed from the separator along line 20 having level control valve 200, reheated against the first flash vapors in heat exchanger [7 and thereafter combined at 21 with the gross demethanizer column overhead stream in line 28.
  • flash liquid taken off in line 15 controlled by level control valve 140 is passed through heat exchanger 2 for warming, e.g. to 75F and is then passed to fractionating column 22 at feed point 23 in the column.
  • Column 22 is operated as the demethanizer first stage. Pressure in bottoms section 24 of column 22 is relatively low for a demethanizing operation e.g. between 200 and 350 psia and suitably about 265 psia. Bottoms temperature is maintained with reboiler loop 25 by condensation of propylene refrigeration vapors from line 26 at a level sufficient to boil the bottoms mixture of C,-C and heavier hydrocarbons e.g. 5F.
  • the upper section 27 of column 22 above the feed point 23 is operated at a slightly lower pressure and at a lower temperature than the column bottom section 24, e.g. at 260 psia and 1 10F. Temperatures in upper section 27 may be between 70 and lF and pressures may range between l95 and 340 psia.
  • the gross demethanizer overhead from column upper section 27 comprising predominantly methane and some minimum quantity of ethylene e.g. 4 to 7 percent is passed along line 28 to rectification in rectifier 29.
  • the gross demethanizer overhead is cooled in heat exchanger 30 with l 47F ethylene prior to introduction into the rectifier 29.
  • the flash liquid from separator 19 is added to the gross demethanizer overhead at point 21 in line 28, following heat exchanger 30.
  • the gross demethanizer overhead is passed into the bottom of rectifier 29 which is suitably maintained at a pressure of 255 psia and a temperature of l40F, both below their corresponding values in upper section 27 of column 22.
  • Liquid bottoms from the rectifier 29 is passed by pump 31 along line 32 through valve 324 to the upper section 27 of demethanizer column 22, as reflux.
  • the overhead from rectifier 29 comprising methane and 2 to 4 percent hydrogen and minimum ethylene eg 0 to 2 percent and preferably 1 percent by weight and typically at a temperature of -l65F is passed along line 33 to a turbo-expander 34 through heat exchanger 46 for warming.
  • the turboexpander includes an expander section 35, typically a centrifugal expander which is operated as an expansion motor and a compressor section 36 also centrifugal, which is operated as a compressor, driven by the expander section to which it is directly coupled, as by a motor.
  • expansion motor herein is used to describe devices producing mechanical energy through gas or vapor expansion. While turbine motors are preferred reciprocating motors may be used.
  • the rectifier overhead line 33 communicates along line 37 with the inlet 38 of expander section and along line 39 with the suction inlet 40 of the compressor section 36, whereby the rectifier overhead vapors in line 33 are divided into two portions, at 41, for passage to either the expander or compressor sections 35, 36 along line 37 or 39 respectively. Moreover, by control valve 42 operation a portion of the rectifier overhead can bypass the expander and pass directly to line ll e.g. in heat exchanger 17 as shown.
  • Post-fractionation compression of a portion of the rectifier overhead vapors provides a capability in the present process for maximum ethylene recovery without operating the fractionation column 22 at critical values of temperature or at unduly high pressure.
  • the rectifier overhead vapors are compressed to a pressure at which the major portion Le. 50 percent by volume and above, e.g. 50 to 75 percent up to 95 percent of the methane component thereof is condensible against readily available streams such as cold ethylene, e.gt ethylene at 147F.
  • Total condensation is not economically feasible due to the necessary inclusion of small concentrations of hydrogen in the methane overhead from rectifier 29, which in turn results from solution of minor amounts of hydrogen in the liquids separated in separators l4 and 19.
  • Suitable pressures in the compressed overhead vapors from compressor operation range between 450 and 600 psia with pressures between 475 and 550 psia being typical.
  • the pressurized vapors generally emerge from the compressor section 35 at a somewhat increased temperature e. g. from to OF.
  • the compressed vapor is passed from compressor section 35 along line 43 to heat exchanger 30 where the compressed vapors are cooled and partially condensed by ethylene refrigeration at l 47F for passage along line 44 to gas liquid separator 45 through heat exchanger 46 providing heat exchange with the rectifier overhead in line 33 which comprises cold methane-rich vapor.
  • the methane overhead from separator 45 is passed along line 47 through pressure control valve 47a to line 33 at point 48 for combination with gross overhead stream to the turboexpander 34.
  • the liquid from separator 45 comprising substantially liquid methane is passed along line 49, controlled by level control valve 490, back to rectifier 29 as reflux at feed point 50, ultimately to be recovered as overhead vapor from rectifier 29 in line 33 or as liquid methane in line 51 to be combined at 52 with expanded methane from expander section 35 leaving the system in line 11.
  • the bottoms from column 22 comprising ethylene together with any heavier ends present in the feed are recovered as bottoms from line 53 having pump 54 and control valve 540.
  • a recovery stream containing by weight about 60 percent ethylene, l0 percent ethane and 30 percent propane, propylene, and heavier hydrocarbons may typically be obtained in line 53.
  • the turbo-expander is illustrative of motor devices which derive energy by gas expansion to do work and which may simultaneously cool the expanding gas.
  • the portion of the rectifier 29 overhead passed to the expander section 36 typically comprises not less than 50 percent by volume of the rectifier overhead, and the portion passed to the com pressor accordingly less than 50 percent.
  • the cooled and expanded overhead vapor portion e.g. at 2 l 8F is passed from expander section 36 along line ll in sequence to heat exchangers l7 and 9 where its refrigeration values are used to cool the feed as above described and ultimately to disposal as fuel gas eg at a temperature of +5 2F.
  • composition data line 1 feed at +60F and 500 psia is cooled to 1 20F at 485 psia. for entry into a first liquid-gas separator 14 with process streams and ethylene and/or propylene refrigerants. Flashed vapor from the -l 20F flash is further cooled in heat exchanger 17 to 2 lOF at 480 psia to secure a hydrogen rich by-product gas in separator 19 which is taken off along line H). Liquid from the 1 20F flash is exchanged against the feed in heat exchanger 2 and fed to the demethanizer column 22 at 75F.
  • Demethanizer column bottom pressure is maintained at 260 psia and the temperature of material therein at $F.
  • Overhead vapors from the demethanizer column 22 at l lF and 255 psia are rectified in rectifier 29.
  • Rectifier overhead vapors at l65F and 250 psia are first heated in exchanger 46 to l47F and then split and less than 50 percent is passed to the intake of compressor 36 to be compressed to 500 psia at -60F.
  • the energy for the compression is obtained from the expansion in expander 36 of the balance (greater than 50 percent) of the rectifier overhead, the expansion being from a pressure of 250 psia and a temperature of l47F to 70 psia and 2 l 8F.
  • the expansion energy is balanced with the compression energy at these conditions.
  • Liquid methane from separator 45 is returned to the rectifier 29 as reflux.
  • a typical material balance for the process is given in the tasure between about 200 and 350 psia a separation overhead of methane-rich vapor, dividing said overhead vapor into two portions, expanding a first portion of the overhead vapor through an expansion motor producing an energy output from the vapor expansion, compressing a second portion of the overhead vapor to a second pressure greater than said first pressure in a compressor driven by the energy output of said motor, cooling the compressed overhead vapor portion sufficiently to condense the major portion of the methane therein, returning the condensed methane to the methane separation zone as reflux and recovering ethylene and heavier components of the feed as bottoms from the methane separation zone.
  • first vapor portion comprises not less than 50 percent by volume of the methane 20 ble. separation overhead.
  • the present process for the removal of methane from a hydrocarbon feed containing ethylene, hydrogen, methane and higher boiling hydrocarbon components with low low of ethylene includes removing hydrogen from the feed, fractionating the hydrogen-lean feed in a column having a bottoms temperature less than about IOF and a bottoms pressure between 250 and 275 psia to provide a methane-rich overhead vapor comprising methane and up to 4 percent by volume hydrogen, and not more than 2 percent by volume ethylene at a temperature below about l40F and a bottoms stream essentially free of methane, dividing said overhead vapor into a first portion equal to not less than 50 percent by volume of the column overhead vapor and a second portion conversely equal to less than 50 percent of the overhead vapor, expanding the first portion through a turbine to lower the pressure of the first portion to less than about 150 psia and to lower the temperature of the first portion to less than about -200F and producing an energy output from the vapor expansion, heat ex
  • Process for the removal of methane from a hydroca'bon feed containing ethylene, methane and higher boiling hydrocarbon components with low loss of ethylene which includes effecting in a methane separation zone at a first prea- 4.
  • Process according to claim I in which said second portion of the overhead vapor is compressed to a pressure above about 450 psia.
  • Process according to claim 6 including also returning the liquid methane obtained from said second vapor portion to the methane separation zone as reflux.
  • Process according to claim I including also centrifugally expanding said first vapor portion through a turbine.
  • Process according to claim 9 including also centrifugally expanding said first vapor portion through a turbine.
  • Process according to claim I] including also cooling the compressed second vapor portion to a temperature liq uefying the methane therein.
  • Process according to claim 13 including also heat exchanging said expanded overhead vapor portion with said feed to cool said feed prior to said flashing.
  • Process according to claim 13 including also heat exchanging the bottoms from the methane separation zone with said feed to cool the feed prior to said flashing.
  • Process for the removal of methane from a hydrocarbon feed containing ethylene, hydrogen, methane and higher boiling hydrocarbon components with low loss of ethylene which includes hydrogen removal from the feed, fractionating said feed in a column having a bottoms temperature less than about 10F and a bottoms pressure between 250 and 275 psia to provide a methane-rich overhead vapor comprising methane, up to 4 percent by volume hydrogen and not more then 2 percent by volume ethylene at a temperature below about I40F and a bottoms stream essentially free of methane; dividing said overhead vapor into a first portion equal to not less than 50 percent by volume of said overhead vapor and a second portion conversely equal to less than 50 percent of said overhead vapor; expanding said first portion through a turbine to lower the pressure of said first portion to less than about 150 psia and to lower the temperature of said first portion to less than about 200F producing an energy output from said vapor expansion, heat exchanging said expanded first portion with said feed to cool the feed to temperature about l20F

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US874842A 1969-11-07 1969-11-07 Low pressure ethylene recovery process Expired - Lifetime US3675435A (en)

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Cited By (43)

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US3827245A (en) * 1971-09-22 1974-08-06 Stone & Webster Eng Corp Recovery and purification of ethylene from direct hydration ethanol vent gas streams
US3956415A (en) * 1974-03-04 1976-05-11 Petrocarbon Developments Limited Plural stage distillation with intermediate indirect heat exchange, of feed streams comprising ethylene and methane
US4002042A (en) * 1974-11-27 1977-01-11 Air Products And Chemicals, Inc. Recovery of C2 + hydrocarbons by plural stage rectification and first stage dephlegmation
US4167402A (en) * 1977-09-16 1979-09-11 Union Carbide Corporation Ethylene separation process
US4270940A (en) * 1979-11-09 1981-06-02 Air Products And Chemicals, Inc. Recovery of C2 hydrocarbons from demethanizer overhead
US4410342A (en) * 1982-05-24 1983-10-18 United States Riley Corporation Method and apparatus for separating a liquid product from a hydrocarbon-containing gas
WO1984003140A1 (en) * 1983-02-01 1984-08-16 Stone & Webster Eng Corp Apparatus and method for recovering light hydrocarbons from hydrogen containing gases
US4496380A (en) * 1981-11-24 1985-01-29 Shell Oil Company Cryogenic gas plant
US4507133A (en) * 1983-09-29 1985-03-26 Exxon Production Research Co. Process for LPG recovery
US4617039A (en) * 1984-11-19 1986-10-14 Pro-Quip Corporation Separating hydrocarbon gases
US4695303A (en) * 1986-07-08 1987-09-22 Mcdermott International, Inc. Method for recovery of natural gas liquids
US4710214A (en) * 1986-12-19 1987-12-01 The M. W. Kellogg Company Process for separation of hydrocarbon gases
US4711651A (en) * 1986-12-19 1987-12-08 The M. W. Kellogg Company Process for separation of hydrocarbon gases
US4718927A (en) * 1985-09-02 1988-01-12 Linde Aktiengesellschaft Process for the separation of C2+ hydrocarbons from natural gas
US4720293A (en) * 1987-04-28 1988-01-19 Air Products And Chemicals, Inc. Process for the recovery and purification of ethylene
USRE33408E (en) * 1983-09-29 1990-10-30 Exxon Production Research Company Process for LPG recovery
US5035732A (en) * 1990-01-04 1991-07-30 Stone & Webster Engineering Corporation Cryogenic separation of gaseous mixtures
US5090977A (en) * 1990-11-13 1992-02-25 Exxon Chemical Patents Inc. Sequence for separating propylene from cracked gases
US5157925A (en) * 1991-09-06 1992-10-27 Exxon Production Research Company Light end enhanced refrigeration loop
US5361589A (en) * 1994-02-04 1994-11-08 Air Products And Chemicals, Inc. Precooling for ethylene recovery in dual demethanizer fractionation systems
US5377490A (en) * 1994-02-04 1995-01-03 Air Products And Chemicals, Inc. Open loop mixed refrigerant cycle for ethylene recovery
US5379597A (en) * 1994-02-04 1995-01-10 Air Products And Chemicals, Inc. Mixed refrigerant cycle for ethylene recovery
US5421167A (en) * 1994-04-01 1995-06-06 The M. W. Kellogg Company Enhanced olefin recovery method
US5442924A (en) * 1994-02-16 1995-08-22 The Dow Chemical Company Liquid removal from natural gas
US6712880B2 (en) 2001-03-01 2004-03-30 Abb Lummus Global, Inc. Cryogenic process utilizing high pressure absorber column
US20050154245A1 (en) * 2003-12-18 2005-07-14 Rian Reyneke Hydrogen recovery in a distributed distillation system
US6931889B1 (en) * 2002-04-19 2005-08-23 Abb Lummus Global, Randall Gas Technologies Cryogenic process for increased recovery of hydrogen
US20060283207A1 (en) * 2005-06-20 2006-12-21 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US20100263407A1 (en) * 2009-04-21 2010-10-21 Henri Paradowski Method for producing a flow which is rich in methane and a cut which is rich in c2+ hydrocarbons from a flow of feed natural gas and an associated installation
US20110167868A1 (en) * 2010-01-14 2011-07-14 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US20130118202A1 (en) * 2011-11-14 2013-05-16 Michael D. Newman Co2 freezing apparatus
US8667812B2 (en) 2010-06-03 2014-03-11 Ordoff Engineers, Ltd. Hydrocabon gas processing
US8794030B2 (en) 2009-05-15 2014-08-05 Ortloff Engineers, Ltd. Liquefied natural gas and hydrocarbon gas processing
US8850849B2 (en) 2008-05-16 2014-10-07 Ortloff Engineers, Ltd. Liquefied natural gas and hydrocarbon gas processing
US20160327336A1 (en) * 2015-05-04 2016-11-10 GE Oil & Gas, Inc. Preparing hydrocarbon streams for storage
US20170248364A1 (en) * 2014-09-30 2017-08-31 Dow Global Technologies Llc Process for increasing ethylene and propylene yield from a propylene plant
CN110173960A (zh) * 2019-06-28 2019-08-27 正和集团股份有限公司 一种富氢气体的回收利用装置及工艺
US10533794B2 (en) 2016-08-26 2020-01-14 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US10551119B2 (en) 2016-08-26 2020-02-04 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US10551118B2 (en) 2016-08-26 2020-02-04 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US11286216B2 (en) * 2018-09-04 2022-03-29 Lg Chem, Ltd. Method for preparing ethylene and apparatus for preparing ethylene
US11428465B2 (en) 2017-06-01 2022-08-30 Uop Llc Hydrocarbon gas processing
US11543180B2 (en) 2017-06-01 2023-01-03 Uop Llc Hydrocarbon gas processing

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JPS5347581U (de) * 1976-09-28 1978-04-22
JPS59121115U (ja) * 1983-02-04 1984-08-15 日立電線株式会社 フラツトケ−ブル
WO1997036139A1 (en) * 1996-03-26 1997-10-02 Phillips Petroleum Company Aromatics and/or heavies removal from a methane-based feed by condensation and stripping
CN103159582B (zh) * 2013-03-21 2015-06-17 杭州杭氧股份有限公司 一种用于丙烷或混合烷烃催化脱氢制丙烯中的低温分离系统及方法
CN115999328A (zh) * 2021-10-22 2023-04-25 中国石油化工股份有限公司 膜分离结合精馏制备乙烯的方法和系统

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US3377811A (en) * 1965-12-28 1968-04-16 Air Prod & Chem Liquefaction process employing expanded feed as refrigerant
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US2817961A (en) * 1954-08-09 1957-12-31 Ethyl Corp Ethylene recovery
US2880592A (en) * 1955-11-10 1959-04-07 Phillips Petroleum Co Demethanization of cracked gases
US3251190A (en) * 1961-10-26 1966-05-17 Linde Eismasch Ag Process and apparatus for obtaining low purity oxygen by fractionation of air at low temperatures
US3261168A (en) * 1961-11-03 1966-07-19 Petrocarbon Dev Ltd Separation of oxygen from air
US3186182A (en) * 1963-05-27 1965-06-01 Phillips Petroleum Co Low-temperature, low-pressure separation of gases
US3292380A (en) * 1964-04-28 1966-12-20 Coastal States Gas Producing C Method and equipment for treating hydrocarbon gases for pressure reduction and condensate recovery
US3292381A (en) * 1964-07-08 1966-12-20 Coastal States Petrochemical C Separation of natural gas by liquefaction with an injected hydrate inhibitor
US3377811A (en) * 1965-12-28 1968-04-16 Air Prod & Chem Liquefaction process employing expanded feed as refrigerant
US3503220A (en) * 1967-07-27 1970-03-31 Chicago Bridge & Iron Co Expander cycle for natural gas liquefication with split feed stream

Cited By (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3827245A (en) * 1971-09-22 1974-08-06 Stone & Webster Eng Corp Recovery and purification of ethylene from direct hydration ethanol vent gas streams
US3956415A (en) * 1974-03-04 1976-05-11 Petrocarbon Developments Limited Plural stage distillation with intermediate indirect heat exchange, of feed streams comprising ethylene and methane
US4002042A (en) * 1974-11-27 1977-01-11 Air Products And Chemicals, Inc. Recovery of C2 + hydrocarbons by plural stage rectification and first stage dephlegmation
US4167402A (en) * 1977-09-16 1979-09-11 Union Carbide Corporation Ethylene separation process
US4270940A (en) * 1979-11-09 1981-06-02 Air Products And Chemicals, Inc. Recovery of C2 hydrocarbons from demethanizer overhead
US4496380A (en) * 1981-11-24 1985-01-29 Shell Oil Company Cryogenic gas plant
US4410342A (en) * 1982-05-24 1983-10-18 United States Riley Corporation Method and apparatus for separating a liquid product from a hydrocarbon-containing gas
WO1984003140A1 (en) * 1983-02-01 1984-08-16 Stone & Webster Eng Corp Apparatus and method for recovering light hydrocarbons from hydrogen containing gases
US4496381A (en) * 1983-02-01 1985-01-29 Stone & Webster Engineering Corp. Apparatus and method for recovering light hydrocarbons from hydrogen containing gases
USRE33408E (en) * 1983-09-29 1990-10-30 Exxon Production Research Company Process for LPG recovery
US4507133A (en) * 1983-09-29 1985-03-26 Exxon Production Research Co. Process for LPG recovery
US4617039A (en) * 1984-11-19 1986-10-14 Pro-Quip Corporation Separating hydrocarbon gases
AU582398B2 (en) * 1984-11-19 1989-03-23 Elkcorp Separating hydrocarbon gases
US4718927A (en) * 1985-09-02 1988-01-12 Linde Aktiengesellschaft Process for the separation of C2+ hydrocarbons from natural gas
US4695303A (en) * 1986-07-08 1987-09-22 Mcdermott International, Inc. Method for recovery of natural gas liquids
US4710214A (en) * 1986-12-19 1987-12-01 The M. W. Kellogg Company Process for separation of hydrocarbon gases
US4711651A (en) * 1986-12-19 1987-12-08 The M. W. Kellogg Company Process for separation of hydrocarbon gases
US4720293A (en) * 1987-04-28 1988-01-19 Air Products And Chemicals, Inc. Process for the recovery and purification of ethylene
US5035732A (en) * 1990-01-04 1991-07-30 Stone & Webster Engineering Corporation Cryogenic separation of gaseous mixtures
US5090977A (en) * 1990-11-13 1992-02-25 Exxon Chemical Patents Inc. Sequence for separating propylene from cracked gases
US5157925A (en) * 1991-09-06 1992-10-27 Exxon Production Research Company Light end enhanced refrigeration loop
SG81846A1 (en) * 1994-02-04 2001-07-24 Air Prod & Chem Precooling for ethylene recovery in dual demethanizer fractionation systems
US5502972A (en) * 1994-02-04 1996-04-02 Air Products And Chemicals, Inc. Mixed refrigerant cycle for ethylene recovery
US5379597A (en) * 1994-02-04 1995-01-10 Air Products And Chemicals, Inc. Mixed refrigerant cycle for ethylene recovery
US5377490A (en) * 1994-02-04 1995-01-03 Air Products And Chemicals, Inc. Open loop mixed refrigerant cycle for ethylene recovery
US5361589A (en) * 1994-02-04 1994-11-08 Air Products And Chemicals, Inc. Precooling for ethylene recovery in dual demethanizer fractionation systems
US5497626A (en) * 1994-02-04 1996-03-12 Air Products And Chemicals, Inc. Open loop mixed refrigerant cycle for ethylene recovery
US5442924A (en) * 1994-02-16 1995-08-22 The Dow Chemical Company Liquid removal from natural gas
US5421167A (en) * 1994-04-01 1995-06-06 The M. W. Kellogg Company Enhanced olefin recovery method
EP2664882A1 (de) 2001-03-01 2013-11-20 Lummus Technology Inc. Kryogenisches Verfahren mit Hochdruckabsorptionssäule
US6712880B2 (en) 2001-03-01 2004-03-30 Abb Lummus Global, Inc. Cryogenic process utilizing high pressure absorber column
US6931889B1 (en) * 2002-04-19 2005-08-23 Abb Lummus Global, Randall Gas Technologies Cryogenic process for increased recovery of hydrogen
US20050154245A1 (en) * 2003-12-18 2005-07-14 Rian Reyneke Hydrogen recovery in a distributed distillation system
US20060283207A1 (en) * 2005-06-20 2006-12-21 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US9080810B2 (en) 2005-06-20 2015-07-14 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US8850849B2 (en) 2008-05-16 2014-10-07 Ortloff Engineers, Ltd. Liquefied natural gas and hydrocarbon gas processing
US8752401B2 (en) 2009-04-21 2014-06-17 Technip France Method for producing a flow which is rich in methane and a cut which is rich in C2+ hydrocarbons from a flow of feed natural gas and an associated installation
US9759481B2 (en) 2009-04-21 2017-09-12 Technip France Method for producing a flow which is rich in methane and a cut which is rich in C2+ hydrocarbons from a flow of feed natural gas and an associated installation
WO2010122256A3 (fr) * 2009-04-21 2013-07-18 Technip France Procédé de production d'un courant riche en méthane et d'une coupe riche en hydrocarbures en c2+ à partir d'un courant de gaz naturel de charge, et installation associée
US20100263407A1 (en) * 2009-04-21 2010-10-21 Henri Paradowski Method for producing a flow which is rich in methane and a cut which is rich in c2+ hydrocarbons from a flow of feed natural gas and an associated installation
FR2944523A1 (fr) * 2009-04-21 2010-10-22 Technip France Procede de production d'un courant riche en methane et d'une coupe riche en hydrocarbures en c2+ a partir d'un courant de gaz naturel de charge, et installation associee
US8794030B2 (en) 2009-05-15 2014-08-05 Ortloff Engineers, Ltd. Liquefied natural gas and hydrocarbon gas processing
US20110167868A1 (en) * 2010-01-14 2011-07-14 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US9021832B2 (en) 2010-01-14 2015-05-05 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US8667812B2 (en) 2010-06-03 2014-03-11 Ordoff Engineers, Ltd. Hydrocabon gas processing
US20130118202A1 (en) * 2011-11-14 2013-05-16 Michael D. Newman Co2 freezing apparatus
US10808999B2 (en) * 2014-09-30 2020-10-20 Dow Global Technologies Llc Process for increasing ethylene and propylene yield from a propylene plant
US20170248364A1 (en) * 2014-09-30 2017-08-31 Dow Global Technologies Llc Process for increasing ethylene and propylene yield from a propylene plant
US10928128B2 (en) * 2015-05-04 2021-02-23 GE Oil & Gas, Inc. Preparing hydrocarbon streams for storage
US20160327336A1 (en) * 2015-05-04 2016-11-10 GE Oil & Gas, Inc. Preparing hydrocarbon streams for storage
US20210172676A1 (en) * 2015-05-04 2021-06-10 GE Oil & Gas, Inc. Preparing hydrocarbon streams for storage
US11988445B2 (en) * 2015-05-04 2024-05-21 GE Oil & Gas, Inc. Preparing hydrocarbon streams for storage
US10533794B2 (en) 2016-08-26 2020-01-14 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US10551119B2 (en) 2016-08-26 2020-02-04 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US10551118B2 (en) 2016-08-26 2020-02-04 Ortloff Engineers, Ltd. Hydrocarbon gas processing
US11428465B2 (en) 2017-06-01 2022-08-30 Uop Llc Hydrocarbon gas processing
US11543180B2 (en) 2017-06-01 2023-01-03 Uop Llc Hydrocarbon gas processing
US11286216B2 (en) * 2018-09-04 2022-03-29 Lg Chem, Ltd. Method for preparing ethylene and apparatus for preparing ethylene
CN110173960A (zh) * 2019-06-28 2019-08-27 正和集团股份有限公司 一种富氢气体的回收利用装置及工艺

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NL7016247A (de) 1971-05-11
FR2069123A5 (de) 1971-09-03
BE758567A (fr) 1971-05-06
DE2053244A1 (de) 1971-05-19
NL151972B (nl) 1977-01-17
GB1291745A (en) 1972-10-04
JPS5146074B1 (de) 1976-12-07
DE2053244B2 (de) 1975-08-07
ES385316A1 (es) 1974-07-16

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