[go: up one dir, main page]

US20120088940A1 - Reflux condenser - Google Patents

Reflux condenser Download PDF

Info

Publication number
US20120088940A1
US20120088940A1 US12/735,491 US73549109A US2012088940A1 US 20120088940 A1 US20120088940 A1 US 20120088940A1 US 73549109 A US73549109 A US 73549109A US 2012088940 A1 US2012088940 A1 US 2012088940A1
Authority
US
United States
Prior art keywords
condenser
vapor stream
tube
tube bundle
formaldehyde
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/735,491
Other languages
English (en)
Inventor
Fred A. Conneway
Clyde L. Rhodes II
John F. Szul
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US12/735,491 priority Critical patent/US20120088940A1/en
Publication of US20120088940A1 publication Critical patent/US20120088940A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
    • B01D5/0063—Reflux condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/04—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping pipe stills
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0003—Condensation of vapours; Recovering volatile solvents by condensation by using heat-exchange surfaces for indirect contact between gases or vapours and the cooling medium
    • B01D5/0012—Vertical tubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/32—Separation; Purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols

Definitions

  • This disclosure relates to a process and system for removing formaldehyde from a vapor stream containing the same. More particularly, this disclosure relates to an improved process for condensing a vapor feed stream containing formaldehyde to remove formaldehyde from the vapor feed stream and recover a desired product.
  • ethylene oxide is prepared by a silver catalyzed, vapor phase, partial oxidation of ethylene with molecular oxygen, a gaseous reaction effluent is obtained.
  • This effluent can be extremely dilute with respect to the desired ethylene oxide product, containing, for example, from about 0.3 mole percent to about 5 mole percent of the desired material.
  • formaldehyde can be removed as an overhead stream following condensation of the ethylene oxide from a stripping column, however, this has several disadvantages. If the formaldehyde concentration in the overhead stream is high, a solid paraformaldehyde phase can form in the overhead system of the column which can result in blockage and erratic operation and can possibly require shutdown and cleanout. See, e.g., J. Frederic Walker, Formaldehyde, pgs. 140-163 (3d Ed. Reinhold Publishing Corp.). On the other hand, in this process, if the overhead stream contains a low formaldehyde concentration, the relative amount of ethylene oxide therein could be excessive, resulting in yield loss of desired purified material.
  • Embodiments of the present disclosure provide processes and apparatuses for removing formaldehyde from a vapor feed stream. Embodiments are adaptable to commercial scale ethylene oxide production.
  • an “ethylene oxide recovery column,” or “column,” refers to, for example, a generally upright, cylindrical column or tower containing plates and/or packing elements, where the plates and packing elements provide a surface area for a liquid and a gas to come into contact, facilitating mass transfer between the liquid and the gas.
  • the column can also have other shapes and general orientations, including a polygonal shaped column that is positioned in a horizontal orientation.
  • the ethylene oxide recovery column includes a stripping portion and a reabsorption portion.
  • the “stripping portion” is the section of the column where one or more components of an aqueous solution are removed by being placed in contact with a gas stream that is largely insoluble in the aqueous solution or by heating the aqueous solution to cause a phase change in the one or more components to be removed.
  • stripping can be performed on the aqueous solution to purify, recover, and/or separate ethylene oxide, where the “aqueous solution” can be defined as a mixture of ethylene oxide, water, and other compounds, in liquid form.
  • the “reabsorbing portion” is the section of the column where components of a gas are removed by contacting the gas with a relatively nonvolatile liquid solvent that absorbs some components of the gas while not absorbing others. Reabsorbing can be employed to remove trace components from gas streams.
  • a “condenser” is a device that converts vapor into liquid.
  • a vapor feed can enter the condenser, where some compounds in the gas phase portion of the first aqueous solution condense while other compounds pass through the condenser and remain in the gas phase.
  • a “reflux condenser” is a condenser where vapor condenses and can flow back into the vessel as a reflux stream.
  • exit entrainment velocity is the velocity of the gas exiting the tube bundle at or above which some of the liquid becomes entrained in the vapor exiting the tube bundle.
  • a “tube sheet” refers to an apparatus that is connected to the tubes in the tube bundle at each end.
  • the tube sheet can serve to hold the tubes in place and physically contain the shell side fluid.
  • FIGS. 1A and 1B provide an illustration of an embodiment of a condenser of the present disclosure.
  • FIG. 2 provides an illustration of an ethylene oxide recovery column of the present disclosure.
  • Embodiments of the present disclosure include methods and apparatuses for removing formaldehyde from a vapor stream introduced into a condenser.
  • the apparatus embodiments include a condenser including elements arranged, sized, and dimensioned to remove at least sixty percent (60%) formaldehyde from a vapor stream to the condenser.
  • Embodiments of the present disclosure remove formaldehyde from a vapor stream entering a condenser.
  • the condenser includes a main body defining a cooling zone, where the main body includes a cooling fluid inlet and a cooling fluid outlet to pass a cooling fluid on a shell side of the condenser, and a generally upright tube bundle disposed in the cooling zone to receive the vapor feed.
  • the tube bundle provides an internal surface area for condensing at least some of the vapor feed as heat is removed by the cooling fluid.
  • the condenser also includes a top tubesheet positioned at a top of the tube bundle, where entrained fluid exiting the tube bundle disengages from the vapor stream, falls on the top tubesheet, and flows down the internal surface area of each tube in the tube bundle to provide a wetted internal surface area.
  • formaldehyde in the vapor feed reacts with water on the wetted internal surface area to form methylene glycol, removing at least sixty percent (60%) of formaldehyde in the vapor stream fed to the condenser.
  • Some embodiments of the present disclosure remove formaldehyde from an aqueous solution containing ethylene oxide, for example, in an ethylene oxide process where ethylene oxide is the desired product.
  • Embodiments of the present disclosure are not limited to ethylene oxide processes, but rather can be used in other processes where the removal of formaldehyde is beneficial.
  • formaldehyde can be beneficial to reduce formaldehyde reactions in refining equipment that can lead to quality problems in a desired product.
  • formaldehyde in an ethylene oxide process, can react in refining equipment to form byproducts (e.g., condensation products) which can lead to failure to meet ultra violet (UV) specifications in refined monoethylene glycol (MEG), an end-use product of ethylene oxide.
  • byproducts e.g., condensation products
  • UV ultra violet
  • MEG refined monoethylene glycol
  • Embodiments of the present disclosure include a shell and tube heat exchanger that condenses a portion of the vapor stream containing formaldehyde entering the heat exchanger, thus, the heat exchanger is termed a condenser.
  • the condenser can consist of a shell with a bundle of tubes inside it. One fluid runs through the tubes, and another fluid flows over the tubes (through the shell) to transfer heat between the two fluids.
  • the set of tubes is called a tube bundle, and may be composed of several types of tubes: plain, longitudinally finned, etc.
  • the condenser can include many tubes, as discussed herein.
  • heat is transferred from the vapor stream entering the condenser to the cooling fluid flowing through the condenser shell side.
  • the temperature of the vapor stream decreases, causing components in the vapor stream to condense into a liquid.
  • the condenser can be designed to maximize the removal of certain components, for example, formaldehyde.
  • the conversion of formaldehyde to methylene glycol is a desired reaction since methylene glycol has a higher boiling point (approximately ninety (90) degrees Celsius (° C.)) as compared to formaldehyde (approximately negative nineteen ( ⁇ 19)° C.). David R. Lide, Handbook of Chemistry and Physics , Pub. 2005, Pages 3-262, 6-41. Thus, methylene glycol will condense into a liquid more readily than formaldehyde, enhancing the removal of formaldehyde from the vapor stream entering the condenser.
  • embodiments of the present disclosure provide methods and apparatuses for maintaining a wetted internal surface area to promote the methylene glycol reaction and to prevent the polymerization reaction.
  • FIG. 1A is an illustration of a condenser 100 according to embodiments of the present disclosure.
  • the condenser 100 can include elements arranged, sized, and dimensioned to remove at least sixty percent (60%) formaldehyde from a vapor stream 102 fed to the condenser 100 .
  • the condenser 100 can remove at least eighty percent (80%) formaldehyde from the vapor stream 102 feed.
  • the condenser 100 can remove at least eighty-five percent (85%) formaldehyde from the vapor stream 102 feed.
  • the condenser 100 includes a main body 104 , or exterior shell, defining a cooling zone 106 .
  • the cooling zone 106 is where heat is transferred from the vapor stream 102 to a cooling fluid 108 .
  • the main body 104 can have a generally circular cross sectional shape. Other shapes are also possible, including ovular, or polygonal.
  • the internal diameter of the main body 104 in embodiments including a circular main body 104 , can range from about one hundred (100) inches (2.54 meters) to about two hundred fifty (250) inches (6.35 meters).
  • the main body 104 includes a cooling fluid inlet 110 and a cooling fluid outlet 112 , where cooling fluid 108 is passed into the cooling fluid inlet 110 to circulate through the main body 104 on a shell side of the condenser 100 .
  • the cooling fluid 108 can be water, however, embodiments are not so limited.
  • the condenser 100 includes a generally upright tube bundle 114 comprised of a number of vertically oriented tubes 116 .
  • the tube bundle 114 is disposed in the cooling zone 106 of the main body 104 .
  • the tube bundle 114 can be affixed in position within the main body 104 using a top tubesheet 118 , a bottom tubesheet 120 , and, in some embodiments, a number of baffles 122 .
  • Other means for supporting the tube bundle 114 are also possible.
  • the tubes 116 in the tube bundle 114 can be spaced apart to permit cooling fluid 108 to circulate between adjacent tubes 116 and remove heat from the tubes 116 .
  • the tubes 116 in the tube bundle 114 can be spaced apart to permit cooling fluid 108 to circulate between adjacent tubes 116 and remove heat from the tubes 116 .
  • FIG. 1B illustrates an embodiment of a cross-section of the tubes 116 as they can be arranged in the tube bundle 114 inside the main body 104 .
  • Other configurations are also possible.
  • the tube bundle 114 has a ratio of total tube internal surface area to tube internal volume of at least approximately 20:1.
  • each tube 116 in the tube bundle 114 can have a length to diameter ratio of at least approximately 150:1.
  • embodiments of the present disclosure include condensers 100 having tubes 116 with an outside diameter in a range of about 0.50 inches (1.27 centimeters (cm)) to about 2.5 inches (6.35 cm) and an internal diameter in a range of about 0.37 inches (0.94 cm) to about 2.37 inches (6.02 cm).
  • the number of tubes 116 in the tube bundle can range from 1,000 to 115,000 depending on the size of the condenser 100 .
  • the length of the tubes 116 can range from, for example, about 21 feet (6.40 meters) to about 40 feet (12.19 meters).
  • the tube length to outside diameter ratio can range from, for example, about 170:1 to about 960:1 and the ratio of total tube internal surface area to tube internal volume can range from about 20:1 to about 130:1. Embodiments of the present disclosure, however, are not limited to these dimensions.
  • the tubes 116 can be formed of a material that can conduct heat through the width of the tubes 116 .
  • the tube material can be chosen to withstand thermal stresses that may occur during operation, for example, due to thermal expansion that can occur at various temperatures and/or stress from high pressures from the fluids themselves.
  • the tubes 116 can also be formed of a material compatible with both the shell side and tube side fluids for long periods under the operating conditions (temperatures, pressures, pH, etc.) to minimize deterioration such as corrosion.
  • the tubes 116 can be held in place within the exterior shell 104 via the top tube sheet 118 and the bottom tubesheet 120 .
  • Various types of additional supports can be provided between the top 118 and bottom tubesheets 120 to further stabilize the tube bundle 114 .
  • These supports can include additional tubesheets, various types of brackets, and/or a number of baffles 122 .
  • the baffles 122 can direct the flow of the cooling fluid 108 through the main body 104 cooling zone 106 .
  • the baffles 120 can range from approximately ten (10) to twenty (20).
  • the bottom tubesheet 120 can have openings which allow the vapor stream 102 to enter the tubes 116 from a condenser inlet 124 .
  • the tubes 116 may extend through the bottom tubesheet 120 .
  • the tubes 116 can have a tapered bottom 126 , as shown in FIG. 1 , discussed further herein.
  • the tubes 116 are connected to the top tubesheet 118 , which permits a portion of the vapor stream, or in some embodiments, an ethylene oxide rich vapor stream, to exit the condenser 100 through a condenser outlet 128 while liquid exiting the tubes 116 can fall onto the top tubesheet 118 and flow back down the interior surface of the tubes 116 .
  • the condenser 100 also includes a condenser inlet 124 and a condenser outlet 128 .
  • a vapor stream 102 including formaldehyde can be introduced into the condenser 100 through the condenser inlet 124 .
  • the vapor stream can enter the tubes 116 .
  • the cooling fluid 108 is introduced to the condenser 100 via cooling fluid inlet 110 , where the cooling fluid flows through the condenser 100 on the shell-side, and exits the condenser 100 via the cooling fluid outlet 112 .
  • the vapor stream 102 flows from the inlet 130 of the tube bundle 114 to the outlet 132 of the tube bundle 114 , a portion of the vapor stream 102 condenses into a liquid.
  • the liquid condensate, or “reflux” flows down the internal surface of the tubes 116 , providing a wetted tube surface.
  • the vapor stream 102 and liquid condensate thus, flow in a countercurrent direction relative each other inside the tubes 116 .
  • the cooling fluid 108 therefore, flows in a countercurrent direction relative to the liquid condensate.
  • a limiting factor in the design and operation of the condenser 100 can occur when vapor velocity at the tube inlet 130 inhibits condensate downflow from the condenser 100 , a concept known as “flooding.”
  • flooding occurs when the liquid is carried upwards by vapor instead of draining out by gravity.
  • a calculated critical flooding velocity refers to the vapor stream velocity at which the vapor stream velocity at the tube inlet 130 inhibits condensate downflow through the tubes 116 in the tube bundle 114 .
  • the inlet and outlet flooding calculations are taken from the computer program Heat Transfer Research, Inc. (HTRI) Xchanger Suite 5.0.
  • the vapor stream velocity is approximately ninety percent (90%) or less of the calculated critical flooding velocity at the inlet 130 of the tube bundle 114 . Additionally, in various embodiments, the vapor stream velocity can be approximately 8.5 feet per second (2.59 meters per second) or less.
  • each tube 114 in the tube bundle 116 can include a tapered bottom portion 126 .
  • the bottom portion 126 of the tube 116 can extend past the bottom tube sheet 120 .
  • the tapered bottom portions 126 increase the effective cross sectional area of the inlet of the tubes 116 .
  • Flooding can also occur at different places within a tube 116 , depending on the vapor stream and liquid condensate flow rates. For example, flooding at the outlet 132 of the tube 116 can also occur, a phenomenon known as droplet entrainment, where vapor leaving the tubes 116 entrains liquid droplets out of the condenser 100 .
  • Embodiments of the present disclosure use a vapor stream flow rate into the tube bundle 114 that provides a vapor stream exit velocity in excess of a critical exit entrainment velocity.
  • the “critical exit entrainment velocity” refers to the velocity of the gas exiting the tube bundle 114 at or above which some of the liquid becomes entrained in the vapor exiting the tube bundle 114 .
  • the vapor stream exit velocity is greater than approximately two hundred percent (200%) of the critical exit entrainment velocity.
  • the vapor stream exit velocity can be at least one hundred fifty percent (150%) of the critical exit entrainment velocity.
  • the vapor stream exit velocity can be operated at a minimum of one hundred percent (100%) of the critical exit entrainment velocity. As the vapor stream exit velocity is decreased below 100% of the critical exit entrainment velocity, it is possible that the entire length of the internal surface area of the tubes 116 would not remain wetted. In such instances, it is possible that formaldehyde can react to form polymers on the internal surface area of the tubes 116 , as discussed herein. Such reactions can cause clogging, or fouling, inside the tubes 116 .
  • the liquid droplets When the liquid droplets get carried out of the tube outlets 132 , the liquid droplets are sprayed out of the top of the tubes 116 , where the liquid droplets can disengage from the vapor and fall onto the top tubesheet 118 .
  • the liquid droplets collect and flow back down the tubes 116 in the tube bundle 114 .
  • the vapor stream velocity can be monitored to provide adequate liquid residence time for the formaldehyde to react with the water. In some embodiments, vapor stream velocity allows for a liquid residence time of at least approximately 0.5 seconds.
  • the removal of formaldehyde can be increased by encouraging the reaction between formaldehyde and water to form methylene glycol.
  • formaldehyde in the vapor stream can react readily with water on the wetted surface to form methylene glycol.
  • methylene glycol has a higher boiling point than formaldehyde, as discussed herein, the methylene glycol produced from the reaction can readily condense into a liquid and drain down the internal surface area of the tubes.
  • the removal of formaldehyde is dependent on the amount of surface area available for reaction and heat transfer.
  • the condenser 100 of the present disclosure can remove at least sixty percent (60%) formaldehyde from the vapor stream.
  • the condenser of the present disclosure can be used in an ethylene oxide process, where formaldehyde is removed from a vapor stream containing ethylene oxide.
  • the condenser can be located inside an ethylene oxide recovery column between a stripping portion and a reabsorbing portion of the column, where the vapor stream is produced in the stripping portion of the column.
  • ethylene oxide Before ethylene oxide can be recovered from the ethylene oxide recovery column, however, several steps can be performed. As described herein, the steps to produce ethylene oxide and to use ethylene oxide in further reactions can occur in one place, for example, in an ethylene oxide processing plant. The various steps, however, can also occur in separate facilities.
  • Alkylenes (olefins) employed in the process of this disclosure can be characterized by the following structural formula (I):
  • R 1 and R 2 are each individually selected from hydrogen and lower monovalent radicals, preferably C 1 -C 6 alkyl radicals including methyl, ethyl, propyl, butyl, and higher homologues having up to six carbon atoms.
  • R 1 and R 2 are each individually selected from hydrogen, methyl, and ethyl. More preferably, each R 1 and R 2 is hydrogen, and the preferred olefin is ethylene.
  • the corresponding alkylene oxides produced in the process of this disclosure are preferably characterized by the following structural formula (II):
  • R 1 and R 2 are identified herein in connection with the reactant olefin.
  • the alkylene oxide is ethylene oxide (i.e., R 1 and R 2 are both hydrogen).
  • Oxygen may be provided to the process as pure molecular oxygen.
  • oxygen may be provided as an oxygen-containing gas, where the gas further contains one or more gaseous components, for example, gaseous diluents such as nitrogen, helium, methane, and argon, which are essentially inert with respect to the oxidation process.
  • gaseous diluents such as nitrogen, helium, methane, and argon
  • a suitable oxygen-containing gas is air.
  • the oxygen-containing gas may contain one or more of the following gaseous components: water, carbon dioxide, and various gaseous promoters and/or gaseous by-product inhibitors, as discussed herein.
  • the relative volumetric ratio of alkylene to oxygen in the feed gas may range in accordance with any of such known conventional values.
  • the volumetric ratio of alkylene to oxygen in the feed may vary from about 2:1 to about 6:1.
  • the quantity of inert gases, diluents, or other gaseous components such as water, carbon dioxide, and gaseous promoters and gaseous by-product inhibitors, may vary in accordance with known conventional ranges as found in the art.
  • the present disclosure is applicable to epoxidation reactions in any suitable reactor, for example, fixed bed reactors, fixed bed tubular reactors, continuous stirred tank reactors (CSTRs), and fluid bed reactors, a wide variety of which are well known in the art.
  • CSTRs continuous stirred tank reactors
  • the desirability of recycling unreacted feed, employing a single-pass system, or using successive reactions to increase ethylene conversion by employing reactors in a series arrangement can also be readily determined by those skilled in the art.
  • alkylene (olefin), preferably ethylene, to alkylene oxide, preferably ethylene oxide can be carried out, for example, by continuously introducing a feed stream containing alkylene (e.g., ethylene) and oxygen, or an oxygen-containing gas, to a catalyst-containing reactor at a temperature of from about two hundred (200) degrees Celsius (° C.) to about three hundred (300)° C., and a pressure which may be in a range of from approximately five (5) atmospheres (five hundred six (506) kilopascals (kPa)) to approximately thirty atmospheres (3040 kPa) depending on the mass velocity and productivity desired. Residence times in large scale reactors can be on the order of about 0.1 to about five (5) seconds.
  • the resulting alkylene oxide, preferably ethylene oxide can then be separated and recovered from the reaction products using further processes.
  • the alkylene oxide produced according to the present disclosure may be converted into alkylene glycols, alkanolamines, and glycol ethers.
  • Ethylene glycol can be used in two applications: as a raw material for poly(ethylene terephthalate) for use in polyester fiber, film, and containers, and as automotive antifreeze. Also, di-, tri-, and tetraethylene glycols are coproducts of ethylene glycol.
  • Ethylene glycol can be produced by the (catalyzed or uncatalyzed) hydrolysis of ethylene oxide.
  • Ethylene oxide hydrolysis can proceed with either acid or base catalysis or uncatalyzed in neutral medium. Acid catalyzed hydrolysis activates the ethylene oxide by protonation for the reaction with water.
  • Base catalyzed hydrolysis results in considerably lower selectivity to ethylene glycol, producing diethylene glycol and higher glycols (e.g., triethylene and tetraethylene glycols) in addition to the ethylene glycol.
  • Ethylene glycol monoethers can be manufactured by the reaction of an alcohol with ethylene oxide.
  • ethanolamine can be manufactured by the reaction of ethylene oxide with ammonia. See, for example, U.S. Pat. No. 4,845,296.
  • the per-pass conversion of ethylene to ethylene oxide can be low (i.e., on the order of one (1) percent or less), producing a mixture containing dilute concentrations of ethylene oxide along with unreacted ethylene and oxygen, aldehydes, acidic impurities, nitrogen, and argon, among others.
  • the aldehydes can include formaldehyde and acetaldehyde.
  • the per-pass conversion of ethylene to ethylene oxide can range from five (5) percent to twenty-five (25) percent.
  • the dilute ethylene oxide mixture obtained can be scrubbed in an absorber with water to form an aqueous solution including ethylene oxide and to thereby separate the ethylene oxide from the unreacted ethylene and oxygen and other gaseous components of the reaction mixture (e.g., carbon dioxide, nitrogen, argon).
  • the remaining separated gaseous materials can be recycled as cycle gas to be mixed with the feedstock of ethylene and pure oxygen.
  • the aqueous solution is then passed to the ethylene oxide recovery column including the condenser of the present disclosure, where the aqueous solution is used to produce an ethylene oxide stream with a higher ethylene oxide weight percent.
  • the ethylene oxide stream can be removed from the column and passed to other equipment in the ethylene oxide processing plant for further purification or for use in other reactions.
  • the ethylene oxide stream can be routed to a glycol unit reactor, where ethylene oxide is converted to ethylene glycol by reaction with water.
  • the ethylene glycol produced can be monoethylene glycol, diethylene glycol, and/or triethylene glycol.
  • FIG. 2 provides an illustration of an embodiment of an ethylene oxide recovery column according to the present disclosure.
  • the column 234 can include the condenser 200 positioned between a stripping portion 236 and a reabsorption portion 238 .
  • the stripping portion 236 can be located in a lower half of the column 234 and the reabsorption portion 238 can be located in an upper half of the column 234 .
  • the ethylene oxide recovery column 234 can have a diameter ranging from, for example, sixty-five (65) centimeters (cm) to six (6) meters (m) and have a height ranging from, for example, six (6) to sixty (60) m or more.
  • the number of tubes in the tube bundle can be limited by the size of the column 234 .
  • the aqueous solution 240 entering the column 234 can include water, ethylene oxide, formaldehyde, and other light gases and impurities.
  • Examples of further possible compounds in the aqueous solution 240 include methane, carbon dioxide, oxygen, nitrogen, argon, acetaldehyde, and ethylene, among others.
  • the vapor stream 202 entering the condenser 200 can include between five (5) and about sixty (60) mole percent ethylene oxide.
  • the condensed liquid 242 leaving the condenser 200 can include ethylene oxide in a range of about one (1) to about twenty (20) mole percent.
  • the vapor stream 202 entering the condenser 200 can also include water in a range of about fifteen (15) to about eighty (80) mole percent, about five (5) to about two thousand (2,000) mole parts per million (ppm) formaldehyde, and about one (1) to about twenty (20) mole percent light gases and other impurities, as discussed herein.
  • the condenser 200 is operated to remove approximately eighty (80) mole percent formaldehyde from the vapor stream 202 entering the condenser 200 .
  • the vapor inlet 202 can enter the condenser 200 at about 124,000 kilograms per hour (kg/hr) at about ninety-three (93) degrees Celsius (° C.) and at a pressure of about nineteen (19) pounds-force per square inch absolute (psia).
  • the condenser 200 thus, can be operated to cool the vapor inlet to about thirty-seven (37)° C. with an approximate pressure drop along the tube side of the condenser 200 of about 0.2 (psi).
  • the cooling water can be supplied to the condenser 200 , as discussed herein, at about 33° C. with a flow of about three million ninety thousand (3,090,000) kg/hr.
  • the aqueous solution 240 produced from absorbing the dilute ethylene oxide mixture in the absorber, as discussed herein, can be introduced to the stripping portion 236 of the column 234 .
  • ethylene oxide can be removed from the aqueous solution 240 by converting a portion of the aqueous solution 240 to a gas phase.
  • the gas phase as used herein, is the portion of the aqueous solution 240 that undergoes a phase change and subsequently enters the condenser 200 of the present disclosure, as the vapor stream 202 .
  • the remaining portion 244 of the aqueous solution 240 including water, ethylene oxide, and other compounds can be removed from the stripping portion 236 and routed back to the absorber, as discussed herein, to collect more ethylene oxide to be brought back to the column 234 in the aqueous solution 240 .
  • the condenser 200 can be located at a top portion of the stripping portion 236 integral with the column 200 .
  • the condensed liquid stream flowing down the internal surface of the tubes in the tube bundle can return directly to the stripping portion 236 , and the ethylene oxide rich vapor stream 246 produced in the condenser 200 can be released at the top of the condenser 200 .
  • the condensed liquid stream 242 flowing into the stripping portion 236 can include approximately eight (8) weight percent ethylene oxide.
  • the ethylene oxide rich vapor stream 246 can be introduced to the reabsorption portion 238 of the column.
  • the reabsorption portion 238 can absorb ethylene oxide in the ethylene oxide rich vapor stream 246 by contacting with a water stream 248 to absorb the ethylene oxide content thereof.
  • the ethylene oxide stream 250 produced in the reabsorption portion 238 can be routed to the glycol unit reactor where ethylene oxide is converted to ethylene glycol by reaction with water.
  • water, in excess in the glycol unit reactor can be distilled away from the ethylene glycol, condensed, and sent back to the column 234 in the form of the water stream 248 to reabsorb more ethylene oxide.
  • the ethylene oxide stream 250 can also be routed for further purification, or for other reactions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US12/735,491 2008-01-25 2009-01-09 Reflux condenser Abandoned US20120088940A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/735,491 US20120088940A1 (en) 2008-01-25 2009-01-09 Reflux condenser

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US6247108P 2008-01-25 2008-01-25
US12/735,491 US20120088940A1 (en) 2008-01-25 2009-01-09 Reflux condenser
PCT/US2009/000121 WO2009094103A1 (en) 2008-01-25 2009-01-09 Reflux condenser

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/000121 A-371-Of-International WO2009094103A1 (en) 2008-01-25 2009-01-09 Reflux condenser

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/590,407 Division US10471371B2 (en) 2008-01-25 2017-05-09 Reflux condenser method

Publications (1)

Publication Number Publication Date
US20120088940A1 true US20120088940A1 (en) 2012-04-12

Family

ID=40548714

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/735,491 Abandoned US20120088940A1 (en) 2008-01-25 2009-01-09 Reflux condenser
US15/590,407 Active 2029-03-20 US10471371B2 (en) 2008-01-25 2017-05-09 Reflux condenser method

Family Applications After (1)

Application Number Title Priority Date Filing Date
US15/590,407 Active 2029-03-20 US10471371B2 (en) 2008-01-25 2017-05-09 Reflux condenser method

Country Status (6)

Country Link
US (2) US20120088940A1 (zh)
EP (1) EP2247355B1 (zh)
CN (1) CN101925387B (zh)
CA (1) CA2712985C (zh)
TW (1) TWI453061B (zh)
WO (1) WO2009094103A1 (zh)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102112188B (zh) * 2008-07-31 2013-08-28 陶氏技术投资有限公司 环氧烷回收系统
US8129551B2 (en) 2008-07-31 2012-03-06 Dow Technology Investments Llc Alkylene oxide recovery systems
WO2010014182A1 (en) * 2008-07-31 2010-02-04 Dow Technology Investments Llc Alkylene oxide purification columns
EA027599B1 (ru) * 2011-06-15 2017-08-31 Хальдор Топсёэ А/С Конденсаторная труба с высокой пропускной способностью для конденсации серной кислоты
CN103908795B (zh) * 2013-12-19 2015-11-25 柳州市京阳节能科技研发有限公司 多功能高效节能速凝罐
CN107376518A (zh) * 2017-08-29 2017-11-24 浙江万好万家智能设备股份有限公司 一种nmp过滤器
BR112020024792A2 (pt) * 2018-06-04 2021-03-02 Brian Ozero um método para recuperação de óxido de etileno
US12141508B2 (en) 2020-03-16 2024-11-12 Washington University Systems and methods for forming micropillar array
USD1009296S1 (en) 2022-06-29 2023-12-26 Rolf Winter Laboratory glassware
US12496535B2 (en) 2022-11-03 2025-12-16 Rolf Winter Laboratory glassware
CN116832466B (zh) * 2023-07-14 2025-08-22 济源市恒通高新材料有限公司 一种甲酯酯化改造的冷凝蒸出塔及其蒸出方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB174569A (en) * 1921-01-25 1923-03-12 Griscom Russell Co An improved apparatus for the fractional condensation of petroleum or other vapors
US2944966A (en) * 1954-02-19 1960-07-12 Allen G Eickmeyer Method for separation of fluid mixtures
US4142578A (en) * 1977-09-12 1979-03-06 Exxon Research & Engineering Co. Heat exchanger impingement protection
US6209624B1 (en) * 1994-08-17 2001-04-03 Gordon M. Cameron Gas-to-gas heat exchangers for use in sulphuric acid plants
US20030221818A1 (en) * 2002-05-28 2003-12-04 Gentry Matthew C. Reflux condenser system for improved fluids separation

Family Cites Families (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB814119A (en) * 1957-04-30 1959-05-27 Du Pont Dehydrating formaldehyde by distillation and partial condensation
US3174262A (en) 1965-03-23 Chemical process and apparatus for recovery of ethylene oxide
US2771473A (en) 1956-11-20 Ethylene oxide recovery
US1361910A (en) 1919-03-28 1920-12-14 Brownferrier Company Evaporator and condenser
GB564646A (en) 1943-03-04 1944-10-06 Distillers Co Yeast Ltd Improvements in or relating to the recovery of ethylene oxide
GB589547A (en) 1943-07-05 1947-06-24 Distillers Co Yeast Ltd Improvements in or relating to the recovery of ethylene oxide from dilute aqueous solutions
US2775600A (en) 1954-06-01 1956-12-25 Nat Res Corp Separation of ethylene oxide from a gaseous mixture containing same
US3165539A (en) 1960-07-08 1965-01-12 Halcon International Inc Recovery of ethylene oxide from a liquid mixture thereof with normally gaseous impurities
US3418338A (en) 1966-02-28 1968-12-24 Halcon International Inc Water extractive distillation of an ethylene oxide stream containing formaldehyde
US3589689A (en) * 1968-10-28 1971-06-29 Eastman Kodak Co Vapor-liquid contact process
US3745092A (en) 1971-01-11 1973-07-10 Shell Oil Co Recovery and purification of ethylene oxide by distillation and absorption
US3729899A (en) 1971-06-23 1973-05-01 Shell Oil Co Recovery of ethylene oxide from admixed inert gaseous components
BE789308A (fr) 1971-10-04 1973-03-27 Shell Int Research Terige oplossingen van etheenoxyde werkwijze voor het concentreren en zuiveren van wa
US4088699A (en) * 1972-08-31 1978-05-09 The Goodyear Tire & Rubber Company Production of aralkyl tertiary hydroperoxides
US3904656A (en) 1973-02-13 1975-09-09 Ppg Industries Inc Process for preparing monoethylene glycol and ethylene oxide
US3964980A (en) 1975-03-24 1976-06-22 Halcon International, Inc. Process for the recovery of ethylene oxide
IT1039745B (it) * 1975-07-08 1979-12-10 Sir Soc Italiana Resine Spa Procedimento per la purificazione di eilende ossido
JPS5212770A (en) 1975-07-18 1977-01-31 Sansei Conveyor Kk Oscillating apparatus for car gondola suspending boom in building clea ning machine
JPS5416416A (en) 1977-07-08 1979-02-07 Nippon Shokubai Kagaku Kogyo Co Ltd Preparation of high purity ethylene glycol
US4134797A (en) 1978-02-21 1979-01-16 Halcon Research & Development Corporation Process for recovery of ethylene oxide containing low levels of aldehydic impurities
FR2553771B1 (fr) 1983-10-19 1986-01-17 Atochem Procede et dispositif pour concentrer des solutions aqueuses d'oxyde d'ethylene
FR2558069B1 (fr) 1984-01-17 1986-04-25 Atochem Procede d'elimination de gaz dissous dans une solution aqueuse d'oxyde d'ethylene
FR2572403B1 (fr) 1984-10-31 1988-07-29 Atochem Procede pour concentrer des solutions aqueuses diluees d'oxyde d'ethylene
US4726826A (en) 1987-07-17 1988-02-23 The M. W. Kellogg Company Method for partial condensation of hydrocarbon gas mixtures
FR2624859B1 (fr) 1987-12-22 1991-03-22 Atochem Procede pour separer l'oxyde d'ethylene d'impuretes aldehydiques
US4848296A (en) 1987-12-23 1989-07-18 Frank Lopez Rotary internal combustion engine
US5273572A (en) * 1992-05-29 1993-12-28 Membrane Technology And Research, Inc. Process for removing an organic compound from water
US5440058A (en) 1994-06-07 1995-08-08 Union Carbide Chemicals & Plastics Technology Corporation Method for separating compounds in process streams
US5529667A (en) 1994-12-01 1996-06-25 Hoechst Celanese Corporation Process for recovering ethylene oxide
US5840932A (en) 1996-05-21 1998-11-24 Shell Oil Company Process for ethylene oxide production
DE19703627A1 (de) 1997-01-31 1998-08-06 Basf Ag Verfahren zur Ehtylenoxid-Reindestillation
US6437199B1 (en) 1999-07-14 2002-08-20 Nippon Shokubai Co., Ltd. Method for production of high-purity monoethylene glycol
US6187973B1 (en) 2000-04-06 2001-02-13 Scientific Design Company, Inc. Glycol purification
US6242655B1 (en) 2000-07-11 2001-06-05 Scientific Design Company, Inc. Glycol purification
JP2002161071A (ja) * 2000-11-28 2002-06-04 Nippon Shokubai Co Ltd 脱水反応生成物の製造方法及びそれに用いられる脱水反応装置
US7294317B2 (en) 2001-02-08 2007-11-13 Sd Lizenzverwertungsgesellschaft Mbh & Co. Exothermic reaction system
FR2833951A1 (fr) 2001-12-21 2003-06-27 Bp Chemicals Snc Procede de fabrication et de recuperation d'oxyde d'ethylene
US8049044B2 (en) 2002-12-23 2011-11-01 Shell Oil Company Remediation process and apparatus
PE20070158A1 (es) 2005-05-10 2007-03-02 Shell Int Research Proceso y dispositivo para recuperar oxido de etileno de un absorbente graso

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB174569A (en) * 1921-01-25 1923-03-12 Griscom Russell Co An improved apparatus for the fractional condensation of petroleum or other vapors
US2944966A (en) * 1954-02-19 1960-07-12 Allen G Eickmeyer Method for separation of fluid mixtures
US4142578A (en) * 1977-09-12 1979-03-06 Exxon Research & Engineering Co. Heat exchanger impingement protection
US6209624B1 (en) * 1994-08-17 2001-04-03 Gordon M. Cameron Gas-to-gas heat exchangers for use in sulphuric acid plants
US20030221818A1 (en) * 2002-05-28 2003-12-04 Gentry Matthew C. Reflux condenser system for improved fluids separation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CECIL H. FOX, FRANK B. JOHNSON, JOHN WHITING, and PETER P. ROLLER, "Formaldehyde Fixation", 1985, The Journal of Histochemistry and Cytochemistry, Vol. 33, No. 8, pp. 845-853 *

Also Published As

Publication number Publication date
EP2247355B1 (en) 2014-03-26
TW200940151A (en) 2009-10-01
CA2712985C (en) 2016-08-09
CA2712985A1 (en) 2009-07-30
EP2247355A1 (en) 2010-11-10
CN101925387B (zh) 2013-11-06
WO2009094103A8 (en) 2010-09-10
US10471371B2 (en) 2019-11-12
TWI453061B (zh) 2014-09-21
WO2009094103A1 (en) 2009-07-30
CN101925387A (zh) 2010-12-22
US20170239590A1 (en) 2017-08-24

Similar Documents

Publication Publication Date Title
US10471371B2 (en) Reflux condenser method
US8053586B2 (en) Alkylene oxide recovery systems
WO2007071739A1 (en) Microchannel apparatus for unit operations following ethylene oxide production
EP2307112B1 (en) System and process for alkylene oxide purification
EP2307111B1 (en) Alkylene oxide purification columns
US20240400480A1 (en) Process and apparatus for the preparation of alkylene glycol
CN102036975B (zh) 环氧烷回收系统
CN102112187B (zh) 环氧烷回收系统

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION