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WO2025128151A1 - Systèmes et procédés de purification d'ammoniac - Google Patents

Systèmes et procédés de purification d'ammoniac Download PDF

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Publication number
WO2025128151A1
WO2025128151A1 PCT/US2024/032613 US2024032613W WO2025128151A1 WO 2025128151 A1 WO2025128151 A1 WO 2025128151A1 US 2024032613 W US2024032613 W US 2024032613W WO 2025128151 A1 WO2025128151 A1 WO 2025128151A1
Authority
WO
WIPO (PCT)
Prior art keywords
stream
ammonia
stripper
water
hydrogen sulfide
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.)
Pending
Application number
PCT/US2024/032613
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English (en)
Other versions
WO2025128151A8 (fr
Inventor
Martin Taylor
Arlin PETERS
Charles Kimtantas
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.)
Bechtel Energy Technologies and Solutions Inc
Original Assignee
Bechtel Energy Technologies and Solutions Inc
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 Bechtel Energy Technologies and Solutions Inc filed Critical Bechtel Energy Technologies and Solutions Inc
Priority to PCT/US2024/032613 priority Critical patent/WO2025128151A1/fr
Priority to EP24901779.9A priority patent/EP4662177A1/fr
Publication of WO2025128151A1 publication Critical patent/WO2025128151A1/fr
Publication of WO2025128151A8 publication Critical patent/WO2025128151A8/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/12—Separation of ammonia from gases and vapours
    • 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
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/38—Steam distillation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/16—Hydrogen sulfides
    • C01B17/167—Separation

Definitions

  • the present invention generally relates to systems and methods for ammonia purification. More particularly, the present invention relates to ammonia purification using a sour water feed stream with a higher concentration of ammonia (NH3) than hydrogen sulfide (H2S) to produce a purified acid gas stream, a purified NH3 vapor stream and an environmentally safe stripped water stream.
  • a sour water feed stream with a higher concentration of ammonia (NH3) than hydrogen sulfide (H2S) to produce a purified acid gas stream, a purified NH3 vapor stream and an environmentally safe stripped water stream.
  • FIGS. 1A and IB a schematic diagram of a conventional tw o-column sour w ater stripping system illustrates the four processing stages.
  • the following pressures and temperatures are exemplary and only for purposes of illustration.
  • the containment levels of H2S and NH3 in the stripped water stream 134 may be tailored to individual requirements and is typically 10-50 ppmw NH3 and 1-25 ppmw H2S.
  • the stripped water stream 134 is available at about 100-200°F.
  • NH3 stripper 106 essentially all NH3 and any remaining H2S are removed from the H2S stripper bottoms stream 130, which leaves the NH3 stripper 106 as an NH3 stripper overheads stream 133.
  • the NH3 stripper overheads stream 133 is sent to an overhead condenser where it is converted to an NH3 vapor stream and an NH3 liquid stream.
  • a knock out drum 139 separates the NH3 vapor stream 140 and the NH3 liquid stream 150.
  • a portion of the NH3 liquid stream 150 is returned as reflux to the NH3 stripper 106 and another portion of the NH3 liquid stream 150 forms the recycle stream 104.
  • a reboiler 141 acts as a heat exchanger to provide the energy required to remove NH3 and any remaining H2S.
  • the NH3 vapor stream 140 is an NH3-rich gas, which may be processed in a variety of ways.
  • the NH3 vapor stream 140 is sent to a water wash 142 to remove residual amounts of H2S and some hydrocarbons. This step is also referred to as water scrubbing, which produces a scrubbed NH3 vapor stream 160. If NH3 recovery is not desired or economic, the scrubbed NH3 vapor stream 160 may be incinerated. In most cases, however, it is desirable to further purify the scrubbed NH3 vapor stream 160 to produce either an anhydrous liquid NH3 stream 170 or an aqueous NH3 stream 180 suitable for commercial use.
  • the scrubbed NH3 vapor stream 160 is sent to a caustic wash 144 to remove residual contaminants including some hydrocarbons.
  • This step is also referred to as caustic scrubbing, which produces a double scrubbed NH3 vapor stream 162 and may be necessary when problems are expected with process upsets, carbon dioxide, or complex sulfur compounds (e.g. mercaptans or disulfides).
  • the double scrubbed NH3 vapor stream 162 may be sent to either a compressor 146 or a refrigeration unit 148 to produce the anhydrous liquid NH3 stream 170, which contains a negligible amount ofH2S (less than 5 ppmw).
  • the anhydrous liquid NH3 stream 170 is available at about 200 psig and 100°F if liquefied by compression and at atmospheric pressure and about -26 F if liquefied by cooling. Cooling water and/or a refrigerant may be used to exchange heat with the double scrubbed NH3 vapor stream 162.
  • the double scrubbed NH3 vapor stream 162 may also be sent to an NH3 absorber 149, which is essentially another water wash, to produce the aqueous NH3 stream 180, which contains a negligible amount of sulfur (no more than about 2ppmw).
  • the aqueous NH3 stream 180 is available at about 35 psig and 100°F.
  • FTGS. 1A-1B are schematic diagrams illustrating a conventional two- column sour water stripping system.
  • FIG. 2 is a schematic diagram illustrating one embodiment of an NH3 purification system capable of producing a purified acid gas stream, a purified NH3 vapor stream and an environmentally safe stripped water stream using a sour water feed stream with a higher concentration of NH3 than H2S.
  • FIG. 3 is a schematic diagram illustrating another embodiment of an NH3 purification system capable of producing a purified acid gas stream, a purified NH3 vapor stream and an environmentally safe stripped water stream using a sour water feed stream with a higher concentration of NH3 than H2S.
  • the systems and methods disclosed herein overcome the disadvantages encountered by conventional NH3 purification processes by using a sour water feed stream with a higher concentration of NH3 than H2S to produce a purified acid gas stream, a purified NH3 vapor stream and an environmentally safe stripped water stream without adding more acid and base.
  • a system for ammonia purification, which comprises: i) an ammonia stripper for separating a sour water feed stream comprising ammonia and hydrogen sulfide into an ammonia stripper vapor stream and an ammonia stripper liquid stream; ii) a first heat exchanger positioned upstream of the ammonia stripper and enclosing a portion of the sour water feed stream and a portion of the ammonia stripper liquid stream for heating the sour water feed stream and cooling the ammonia stripper liquid stream to produce a stripped water stream; iii) a second heat exchanger for converting the ammonia stripper vapor stream to a two-phase ammonia stream; iv) a knock-out drum for separating the two-phase ammonia stream into an ammonia vapor stream and an ammonia liquid stream; and v) a water wash for removing hydrogen sulfide and carbon dioxide from the ammonia vapor stream and producing
  • a method for ammonia purification which comprises: i) heating a sour water feed stream comprising ammonia and hydrogen sulfide in a heat exchanger using an ammonia stripper liquid stream to produce a heated sour water feed stream; ii) cooling the ammonia stripper liquid stream in the heat exchanger using the sour water feed stream to produce a stripped water stream; iii) separating the heated sour water feed stream into an ammonia stripper vapor stream and an ammonia stripper liquid stream; iv) converting the ammonia stripper vapor stream to a two-phase ammonia stream; v) separating the two-phase ammonia stream into an ammonia vapor stream and an ammonia liquid stream; and vi) removing hydrogen sulfide and carbon dioxide from the ammonia vapor stream to produce a purified ammonia vapor stream and a rich water stream comprising hydrogen sulfide and carbon dioxide.
  • a system for ammonia purification, which comprises: i) an ammonia stripper for separating a sour water feed stream comprising ammonia and hydrogen sulfide into an ammonia stripper vapor stream and an ammonia stripper liquid stream; ii) a first heat exchanger positioned upstream of the ammonia stripper and enclosing a portion of the sour water feed stream and a portion of the ammonia stripper liquid stream for heating the sour water feed stream and cooling the ammonia stripper liquid stream to produce a stripped water stream; iii) a cooler for cooling another ammonia stripper liquid stream withdrawn from the ammonia stripper above the ammonia stripper liquid stream; iv) a pump for pumping a portion of the another ammonia stripper liquid stream back to the ammonia stripper; and v) a water wash for removing hydrogen sulfide and carbon dioxide from the ammonia stripper vapor stream and producing
  • a method for ammonia purification comprises: i) heating a sour water feed stream comprising ammonia and hydrogen sulfide in a heat exchanger using an ammonia stripper liquid stream to produce a heated sour water feed stream; ii) cooling the ammonia stripper liquid stream in the heat exchanger using the sour water feed stream to produce a stripped water stream; iii) separating the heated sour water feed stream in an ammonia stripper into an ammonia stripper vapor stream and an ammonia stripper liquid stream; iv) withdrawing another ammonia stripper liquid stream from the ammonia stripper; v) cooling the another ammonia stripper liquid stream; and vi) removing hydrogen sulfide and carbon dioxide from the ammonia stripper vapor stream to produce a purified ammonia vapor stream and a rich water stream comprising hydrogen sulfide and carbon dioxide.
  • FIG. 2 a schematic diagram illustrates one embodiment of an NH3 purification system 200 capable of producing a purified acid gas stream 274, a purified NH3 vapor stream 242 and an environmentally safe stripped water stream 237 using a sour water feed stream 202 with a higher concentration of NH3 than H2S.
  • a sour water feed stream 202 is mixed with a cooled H2S stripper liquid stream 278 and, optionally, an NH3 liquid stream 230.
  • the mixed stream is then passed through a degasser 208 where dissolved hydrogen (H2), methane (CH4), other light hydrocarbons, H2S and CO2 may be removed through a hydrocarbon vapor stream 205 to produce a degassed sour water feed stream 209.
  • the degassed sour water feed stream 209 is sent to a deoiler 203, which removes free oil from the degassed sour water feed stream 209 to produce a degassed/deoiled sour water feed stream 207.
  • the degassed/deoiled sour water feed stream 207 is sent by means of a first pump 206 to a feed preparation tank 210, which serves to attenuate flow rate and composition changes while also providing the opportunity to remove entrained oil and solids.
  • the feed preparation tank 210 produces a processed sour water feed stream 211, which is sent to a feed coalescer unit 212 by means of a second pump 213.
  • the feed coalescer unit 212 filters solids remaining in the processed sour water feed stream 211 and further separates entrained oil to produce a deoiled sour water feed stream 215.
  • the deoiled sour water feed stream 215 is sent to a feed/product exchanger 214, which acts as a heat exchanger to heat the deoiled sour water feed stream 215 and cool an NH3 stripper liquid stream 232 to produce a heated/ deoiled sour water feed stream 216 and an environmentally safe stripped water stream 234 that may be further cooled by a first heat exchanger 235 using a coolant to produce a chilled stripped water stream 237.
  • the chilled stripped water stream 237 may be discharged to the environment and/or reused. In this manner, the components comprising the NH3 stripper liquid stream 232 and the stripped water stream 234 are effectively the same but may have different pressures and/or temperatures.
  • the components comprising the deoiled sour water feed stream 215 and the heated/deoiled sour water feed stream 216 are effectively the same but may also have different pressures and/or temperatures.
  • the heated/deoiled sour water feed stream 216 may be further processed by NH3 stripping.
  • the heated/deoiled sour water feed stream 216 may be sent to an NH3 stripper 218, which is a steam re-boiled, refluxed distillation column. Essentially all the NH3 and any remaining H2S and CO2 are separated from the heated/deoiled sour water feed stream 216 in the NH3 stripper 218, which produces the NH3 stripper liquid stream 232 and an NH3 stripper vapor stream 220.
  • the NH3 stripper liquid stream 232 leaves the bottom of the NH3 stripper 218 and is sent to the feed/product exchanger 214.
  • the contaminant levels of H2S, CO2 and NH3 in the stripped water stream 234 may be tailored to individual requirements and is typically 10-50 ppmw NH3, 1-25 ppmw H2S and essentially no CO2.
  • the stripped water stream 234 is available at about 100-200°F.
  • NH3 stripper vapor stream 220 leaves the top of the NH3 stripper 218 and is sent to a second heat exchanger 222 where a coolant is used to convert the NH3 stripper vapor stream 220 to a two phase NH3 stream 224 that is sent to a knock-out drum 226.
  • the knock-out drum 226 separates the two phase NH3 stream 224 into an NH3 vapor stream 228 and the NH3 liquid stream 230.
  • a portion of the NH3 liquid stream 230 is returned as reflux to the NH3 stripper 218 and another portion of the NH3 liquid stream 230 may be, optionally, recycled back to mix with the sour water feed stream 202 and the cooled H2S stripper liquid stream 278 using a third pump 236.
  • a reboiler 238 acts as a heat exchanger to provide the energy required to remove NH3 and any remaining H2S.
  • the NH3 vapor stream 228 is an NH3- rich gas, which is further processed.
  • the NH3 vapor stream 228 may be sent to a water wash 240 for purification and to preferentially remove residual amounts of H2S and some hydrocarbons.
  • the water wash 240 produces a purified NH3 vapor stream 242 and a rich water stream 244 comprising H2S and CO2.
  • the rich water stream 244 may be pumped using a fourth pump 246 i) through a third heat exchanger 262 back to the water wash 240 and/or ii) optionally through another feed/product exchanger 264 for further processing.
  • the third heat exchanger 262 uses a coolant to chill the recycled rich water stream 244 pumped back to the water wash 240.
  • Counterflow of the NH3 vapor stream 228 and the chilled stripped water stream 237 removes a majority of the H2S and CO2.
  • the NH3 vapor stream 228, the chilled stripped water stream 237 and the rich water stream 244 entering the water wash 240 may each be divided into two or more streams that enter the water wash 240 at different locations for optimizing the counterflow and removing a majority of the H2S and CO2.
  • the feed/product exchanger 264 acts as a heat exchanger to heat the rich water stream 244 and cool an H2S stripper liquid stream 276 to produce a heated rich water stream 248 and the cooled H2S stripper liquid stream 278.
  • the heated rich water stream 248 comprising NH3, H2S and CO2 may be sent to an H2S stripper 266 to separate the H2S and CO2 from the water.
  • the heated rich water stream 248 that enters the H2S stripper may be divided into two or more streams that enter the H2S stripper 266 at different locations.
  • the H2S stripper 266 contains trays or packing that the heated rich water stream 248 flows through and around to separate H2S and CO2 from the heated rich water stream 248.
  • the chilled stripped water stream 237 may be used to remove NH3 from the exiting vapors.
  • a reboiler 268 acts as a heat exchanger to provide the energy required to i) heat the heated rich water stream 248 and the chilled stripped water stream 237 to preferred temperatures; and ii) strip out H2S and CO2 from the heated rich water stream 248.
  • the H2S stripper 266 produces an H2S stripper vapor stream 270, which is sent to a knock-out drum 272 to substantially remove any entrained droplets and produce a purified acid gas stream 274. Because the acid gas stream 274 contains negligible NH3 (less than 50 ppmw) and very little hydrocarbons, it is an excellent feed for a sulfur recovery unit (SRU) or a sulfuric acid plant.
  • SRU sulfur recovery unit
  • the acid gas stream 274 is available at about 50-200 psig and 100-120°F.
  • the H2S stripper 266 also produces the H2S stripper liquid stream 276, which contains NH3, H2S and CO2 from the bottom of an H2S stripper 266.
  • FIG. 3 a schematic diagram illustrates another embodiment of an NH3 purification system 300 capable of producing a purified acid gas stream 274, a purified NH3 vapor stream 242 and an environmentally safe stripped water stream 237 using a sour water feed stream 202 with a higher concentration of NH3 than H2S.
  • the NH3 purification system 300 is a modification of the NH3 purification system 200 illustrated in FIG. 2 and, therefore, includes many of the same components.
  • the NH3 stripper vapor stream 220 may be sent directly to the water wash 240 for purification in the same manner as the NH3 vapor stream 228 described in reference to FIG. 2.
  • a pump-around subsystem design may be used with the NH3 stripper 218 instead of the overhead condensing subsystem design illustrated in FIG. 2.
  • the pump-around subsystem uses a third pump 302 to pump another NH3 stripper liquid stream 304 from the NH3 stripper 218 through a cooler 306 that produces a cooled NH3 stripper liquid stream 308.
  • the cooled NH3 stripper liquid stream 308 is recycled back to the NH3 stripper 218 and, optionally, to the cooled H2S stripper liquid stream 278 where it is mixed thus, forming a combined liquid stream 310 comprising NH3 and H2S.
  • the sour water feed stream 202 may, therefore, be mixed with the cooled H2S stripper liquid stream 278 or, optionally, the combined liquid stream 310.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

Abstract

Systèmes et procédés de purification de NH3 utilisant un flux d'alimentation en eau acide ayant une concentration plus élevée en NH3 qu'en H2S pour produire un flux gazeux acide purifié, un flux de vapeur de NH3 purifié et un flux d'eau épuré sans danger pour l'environnement sans ajouter davantage d'acide et/ou de base.
PCT/US2024/032613 2024-06-05 2024-06-05 Systèmes et procédés de purification d'ammoniac Pending WO2025128151A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US2024/032613 WO2025128151A1 (fr) 2024-06-05 2024-06-05 Systèmes et procédés de purification d'ammoniac
EP24901779.9A EP4662177A1 (fr) 2024-06-05 2024-06-05 Systèmes et procédés de purification d'ammoniac

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2024/032613 WO2025128151A1 (fr) 2024-06-05 2024-06-05 Systèmes et procédés de purification d'ammoniac

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WO2025128151A1 true WO2025128151A1 (fr) 2025-06-19
WO2025128151A8 WO2025128151A8 (fr) 2025-09-12

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4424115A (en) * 1982-04-09 1984-01-03 Shionogi & Co., Ltd. Selective removal and recovery of ammonia and hydrogen sulfide
US8623314B2 (en) * 2011-07-01 2014-01-07 Alstom Technology Ltd Chilled ammonia based CO2 capture system with ammonia recovery and processes of use
US9605220B2 (en) * 2014-06-28 2017-03-28 Saudi Arabian Oil Company Energy efficient gasification based multi generation apparatus employing advanced process schemes and related methods
US20180326347A1 (en) * 2015-06-10 2018-11-15 Bechtel Hydrocarbon Technology Solutions, Inc. Systems and methods for high co2 ammonia purification
US10427948B2 (en) * 2018-01-26 2019-10-01 Ethan J. Novek Systems and methods for ammonia recovery, acid gas separation, or combination thereof
US11326110B2 (en) * 2020-03-13 2022-05-10 Haldor Topsøe A/S Process and plant for producing hydrocarbons with reduced CO2-footprint and improved hydrogen integration
US20220194794A1 (en) * 2020-12-18 2022-06-23 Uop Llc Process for managing hydrogen sulfide in a refinery

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4424115A (en) * 1982-04-09 1984-01-03 Shionogi & Co., Ltd. Selective removal and recovery of ammonia and hydrogen sulfide
US8623314B2 (en) * 2011-07-01 2014-01-07 Alstom Technology Ltd Chilled ammonia based CO2 capture system with ammonia recovery and processes of use
US9605220B2 (en) * 2014-06-28 2017-03-28 Saudi Arabian Oil Company Energy efficient gasification based multi generation apparatus employing advanced process schemes and related methods
US20180326347A1 (en) * 2015-06-10 2018-11-15 Bechtel Hydrocarbon Technology Solutions, Inc. Systems and methods for high co2 ammonia purification
US10427948B2 (en) * 2018-01-26 2019-10-01 Ethan J. Novek Systems and methods for ammonia recovery, acid gas separation, or combination thereof
US11326110B2 (en) * 2020-03-13 2022-05-10 Haldor Topsøe A/S Process and plant for producing hydrocarbons with reduced CO2-footprint and improved hydrogen integration
US20220194794A1 (en) * 2020-12-18 2022-06-23 Uop Llc Process for managing hydrogen sulfide in a refinery

Also Published As

Publication number Publication date
EP4662177A1 (fr) 2025-12-17
WO2025128151A8 (fr) 2025-09-12

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