US20200071250A1 - Divalent cation removal from rich monoethylene glycol (meg) feed streams by ion exchange - Google Patents
Divalent cation removal from rich monoethylene glycol (meg) feed streams by ion exchange Download PDFInfo
- Publication number
- US20200071250A1 US20200071250A1 US16/661,599 US201916661599A US2020071250A1 US 20200071250 A1 US20200071250 A1 US 20200071250A1 US 201916661599 A US201916661599 A US 201916661599A US 2020071250 A1 US2020071250 A1 US 2020071250A1
- Authority
- US
- United States
- Prior art keywords
- meg
- regeneration
- ion exchange
- brine
- regeneration brine
- 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
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
- B01D15/362—Cation-exchange
-
- 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
- B01D3/06—Flash distillation
-
- 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
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- 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
- C07C31/202—Ethylene glycol
Definitions
- This invention relates to systems and processes designed to treat monoethylene glycol (MEG) used in the oil and gas industry, especially in offshore locations, to control the formation of hydrates. More particularly, the invention relates to MEG reclamation or regeneration processes that are designed to remove divalent cations from a rich MEG feed stream.
- MEG monoethylene glycol
- lean (dry) MEG is mixed with the water in a produced stream to control the formation of hydrates within the stream.
- the now rich (wet) MEG is, in turn, dried 25 by way of a MEG reclamation or MEG regeneration process so that the MEG can be re-used in hydrate control.
- the lean MEG cannot be recovered by simply distilling the rich MEG and water in conditions of high salt concentration because the rich MEG is loaded with dissolved salt ions from the produced water.
- Sodium chloride is commonly the most concentrated salt in the produced water, but it may also contain dissolved divalent salts of magnesium, calcium, strontium, and barium. If these divalent cations are not removed or controlled at a low concentration, their high solubility in MEG will alter the physical properties of the MEG, eventually leading to failure of the reclamation or regeneration process.
- the ions react with carbonate or hydroxide anions to form insoluble salt crystals, which are then removed from the feed stream.
- This process generally requires the addition of caustic and acid to completely remove the divalent cations and to neutralize the feed stream before it enters the MEG reclamation or MEG regeneration process.
- the time and temperature of the current separation process must be strictly controlled.
- the process requires large and expensive equipment, as well as additional chemicals that are not inherently available as part of the MEG reclamation or MEG regeneration process. These chemicals must be obtained from outside sources which can be very expensive, particularly when delivered to offshore platforms in remote parts of the world. The chemicals may also be a safety concern, require specialized handling and storage, and increase training, reporting, and record.keeping requirements.
- the current separation process also produces a carbonate salt in the form of a solid or slurry material that is generally insoluble and requires disposal as a waste. Proper disposal of this material can be expensive, time-consuming, and labor-intensive. Disposal is even more difficult in offshore applications where temporary storage space and transportation to an approved disposal site are not readily available.
- a system for removing divalent cations from a rich MEG feed stream includes an ion exchange bed containing a cation exchange resin that adsorbs the divalent cations in the rich MEG feed stream as it flows through the bed.
- the feed stream flows through a flash separator and a distillation column to reclaim MEG.
- the feed stream flows through a distillation column to regenerate MEG.
- the spent cation exchange resin may be regenerated, without removing it from the ion exchange bed, using a regeneration brine.
- the regeneration brine may be comprised of distilled water that is produced during the MEG reclamation or MEG regeneration process.
- the regeneration brine may also be comprised of sodium chloride that is produced during the MEG reclamation process.
- the regeneration brine may be disposed of as waste or recycled to the brine storage tank and re-used to regenerate the cation exchange resin.
- a process for removing divalent cations from a rich MEG feed stream includes the steps of providing an ion exchange bed containing a cation exchange resin and passing the rich MEG feed stream through the bed so that the divalent cations are adsorbed to the resin.
- the process may also include the step of MEG reclamation or MEG regeneration.
- a regeneration brine may be used to regenerate the spent cation exchange resin without removing it from the ion exchange bed.
- the regeneration brine may be comprised of distilled water produced during the MEG reclamation or MEG regeneration process.
- the regeneration brine may also be comprised of sodium chloride that is produced during the MEG reclamation process. After use, the regeneration brine may be disposed of as waste or recycled to the brine storage tank and re-used to regenerate the cation exchange resin.
- the objects of this invention are to (1) provide a more efficient process to remove divalent cations contained in a rich MEG feed stream before the stream enters a MEG reclamation or MEG regeneration process; (2) simplify the removal process by eliminating required conditions for time and temperature; (3) reduce the volume, footprint, and cost of the processing equipment typically required to remove divalent cations from the rich MEG feed stream; (4) provide a renewable or reusable bed for divalent cation removal; (5) provide a process for physical separation of the divalent cations from the rich MEG feed stream, thus eliminating the need for additional chemicals; and (6) facilitate the disposal of waste streams.
- FIG. 1 presents an embodiment of a process for removing divalent cations from a rich MEG feed stream as part of a MEG reclamation process, practiced according to this invention.
- FIG. 2 presents an embodiment of a process for removing divalent cations from a rich MEG feed stream as part of a MEG regeneration process, practiced according to this invention.
- An ion exchange process may be used to remove divalent cations from the rich MEG feed stream before the feed stream enters the MEG reclamation process, as shown in FIG. 1 , or the MEG regeneration process, as shown in FIG. 2 .
- This ion exchange process is different than conventional water treatment because the rich MEG feed stream is more viscous than water and 25 interacts differently with the ion exchange resins.
- the ion exchange resins of the present invention are subject to higher concentrations of sodium and calcium than would generally be found in water treatment systems.
- a preferred embodiment of a divalent cation removal process 10 A practiced according to this invention begins with the rich MEG feed stream 15 , which is a mixture of produced water and MEG.
- the rich MEG feed stream 15 is routed to a divalent cation removal step comprised of dual ion exchange beds 20 which contain a strong cation exchange resin in the sodium form and alternate between adsorption and regeneration phases.
- the resin removes divalent cations from the rich MEG feed stream 15 by adsorbing the divalent cations from the produced water and displacing the sodium cations.
- two ion exchange beds 20 are shown in FIG. 1 , the ion exchange process may use more than two beds or a single bed.
- the rich MEG stream with the majority of divalent cations removed 25 then exits the ion exchange beds 20 and flows to the MEG reclamation process.
- the MEG reclamation process begins in a flash separator 30 , where the pressure is reduced in order to separate salts from the rich MEG and water.
- a sodium chloride waste stream 35 exits the bottom end of the flash separator 30 , while the vaporized water and MEG stream 40 exits the top end and flows to the distillation column 45 .
- the distillation column 45 uses partial condensation to separate the water and MEG components of the vaporized water and MEG stream 40 .
- Lean MEG 50 exits the bottom end of the distillation column 45 and distilled water 55 is discharged from the top end of the distillation column 45 . After meeting necessary quality requirements, the distilled water 55 may be discharged as waste or recycled to the brine storage tank 60 .
- Regeneration of the ion exchange beds 20 may be accomplished with water containing large amounts of a salt.
- the sodium chloride waste stream 35 from the flash separator 30 is combined with distilled water 55 from the distillation column 45 in the brine storage tank 60 to form regeneration brine 65 .
- one of the ion exchange beds 20 is taken off-line by diverting the flow of the rich MEG feed stream 15 from that bed 20 to the alternate bed 20 .
- a stream of regeneration brine 65 from the brine storage tank 60 is then routed through the off-line ion exchange bed 20 in a direction opposite that of the flow of the rich MEG feed stream 15 .
- the waste stream of sodium chloride and calcium chloride brine 70 can be disposed of as waste or re-used to regenerate the ion exchange beds 20 .
- an ion exchange process may also be used to regenerate MEG by removing divalent cations from the rich MEG feed stream.
- This process may be used in applications where the produced water is relatively free of salts and the purity standards for MEG are less stringent.
- the MEG may contain divalent cations at a concentration that would cause equipment and scaling issues. Removing these ions protects downstream equipment and extends the useful life of the MEG.
- a preferred embodiment of a divalent cation removal process 10 B practiced according to this invention begins with a rich MEG feed stream 85 , which is routed to a divalent cation removal step.
- the divalent cation removal step is comprised of dual ion exchange beds 20 which contain a strong cation exchange resin in the sodium form and alternate between adsorption and regeneration phases. In the adsorption phase, the resin removes divalent cations from the feed stream 85 by adsorbing the divalent cations from the produced water and displacing the sodium cations.
- two ion exchange beds 20 are shown in FIG. 2 , the ion exchange process may use more than two beds or a single bed.
- the rich MEG stream with the majority of divalent cations removed 90 then exits the ion exchange beds 20 and flows to a distillation column 45 , which separates the water from the lean MEG.
- Lean MEG 50 exits the bottom end of the distillation column 45 , while the vaporized water 95 exits the top end. After the vaporized water 95 cools, it may be discharged as waste or recycled to the brine storage tank 60 .
- Regeneration of the ion exchange beds 20 may be accomplished with water containing large amounts of a salt.
- sodium chloride 80 from an external source is combined with the water 95 from the distillation column 45 in the brine storage tank 60 to form regeneration brine 65 .
- one of the ion exchange beds 20 is taken off-line by diverting the flow of the rich MEG feed stream 85 from that bed 20 to the alternate bed 20 .
- a stream of regeneration brine 65 from the brine storage tank 60 is then routed through the off-line ion exchange bed 20 in a direction opposite that of the flow of the feed stream 85 .
- the waste stream of sodium chloride and calcium chloride brine 70 can be disposed of as waste or re-used to regenerate the ion exchange beds 20 .
- the present invention allows the MEG to remain in service for a longer period of time before the concentration of divalent cations increases to a level that could cause scaling or corrosion of the equipment.
- Another advantage of the present invention is that distilled water, which is produced during MEG reclamation and MEG regeneration and conventionally managed as a waste material, is recycled to form regeneration brine.
- Sodium chloride produced during MEG reclamation can also be recycled to form regeneration brine.
- Another advantage is that the waste stream of sodium chloride and calcium chloride brine from regeneration of the ion exchange beds contains only the salts that were originally present in the produced water. As a result, this waste stream can be discharged, if the appropriate water quality standards are met, to the marine environment or an injection well. This waste stream may also be recycled through the regeneration process for the cation exchange resin in the ion exchange beds until the concentration of divalent cations increases to a level that impairs regeneration of the resin.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
A system and process for removing divalent cations from a rich MEG feed stream is presented. An ion exchange bed containing a cation exchange resin adsorbs the divalent cations in the rich MEG feed stream as it flows through the ion exchange bed. After the divalent ions have been removed, the feed stream flows through a flash separator and a distillation column to reclaim MEG. Alternatively, the feed stream flows through a distillation column to regenerate MEG. The spent cation exchange resin may be regenerated in place using a regeneration brine comprised of sodium chloride and water. After use, the regeneration brine may be disposed as waste or recycled to the brine storage tank and re-used to regenerate the cation exchange resin.
Description
- This application is a continuation application of U.S. patent application Ser. No. 15/254,125 filed Sep. 1, 2016, which is a continuation of Ser. No. 13/593,734, filed Aug. 24, 2012, now U.S. Pat. No. 9,433,875, issued Sep. 6, 2016. All cross-referenced applications listed herein are incorporated by reference in their entirety.
- This invention relates to systems and processes designed to treat monoethylene glycol (MEG) used in the oil and gas industry, especially in offshore locations, to control the formation of hydrates. More particularly, the invention relates to MEG reclamation or regeneration processes that are designed to remove divalent cations from a rich MEG feed stream.
- In the oil and gas industry, lean (dry) MEG is mixed with the water in a produced stream to control the formation of hydrates within the stream. The now rich (wet) MEG is, in turn, dried 25 by way of a MEG reclamation or MEG regeneration process so that the MEG can be re-used in hydrate control. The lean MEG cannot be recovered by simply distilling the rich MEG and water in conditions of high salt concentration because the rich MEG is loaded with dissolved salt ions from the produced water. Sodium chloride is commonly the most concentrated salt in the produced water, but it may also contain dissolved divalent salts of magnesium, calcium, strontium, and barium. If these divalent cations are not removed or controlled at a low concentration, their high solubility in MEG will alter the physical properties of the MEG, eventually leading to failure of the reclamation or regeneration process.
- In the current process for separating divalent cations from the rich MEG feed stream, the ions react with carbonate or hydroxide anions to form insoluble salt crystals, which are then removed from the feed stream. This process generally requires the addition of caustic and acid to completely remove the divalent cations and to neutralize the feed stream before it enters the MEG reclamation or MEG regeneration process.
- The time and temperature of the current separation process must be strictly controlled. In addition, the process requires large and expensive equipment, as well as additional chemicals that are not inherently available as part of the MEG reclamation or MEG regeneration process. These chemicals must be obtained from outside sources which can be very expensive, particularly when delivered to offshore platforms in remote parts of the world. The chemicals may also be a safety concern, require specialized handling and storage, and increase training, reporting, and record.keeping requirements. The current separation process also produces a carbonate salt in the form of a solid or slurry material that is generally insoluble and requires disposal as a waste. Proper disposal of this material can be expensive, time-consuming, and labor-intensive. Disposal is even more difficult in offshore applications where temporary storage space and transportation to an approved disposal site are not readily available.
- A need exists for systems and processes for removing divalent cations from rich MEG feed streams in order to improve the efficiency of the MEG reclamation or MEG regeneration process and to prevent the accumulation of salts inside the process equipment. A need also exists for systems and processes that are less expensive, easier to operate, do not require large amounts of space or additional chemicals, and facilitate the disposal of process waste streams.
- A system for removing divalent cations from a rich MEG feed stream is presented. The system includes an ion exchange bed containing a cation exchange resin that adsorbs the divalent cations in the rich MEG feed stream as it flows through the bed. After the divalent cations have been removed, the feed stream flows through a flash separator and a distillation column to reclaim MEG. Alternatively, the feed stream flows through a distillation column to regenerate MEG. The spent cation exchange resin may be regenerated, without removing it from the ion exchange bed, using a regeneration brine. The regeneration brine may be comprised of distilled water that is produced during the MEG reclamation or MEG regeneration process. The regeneration brine may also be comprised of sodium chloride that is produced during the MEG reclamation process. After use, the regeneration brine may be disposed of as waste or recycled to the brine storage tank and re-used to regenerate the cation exchange resin.
- A process for removing divalent cations from a rich MEG feed stream is also presented. The process includes the steps of providing an ion exchange bed containing a cation exchange resin and passing the rich MEG feed stream through the bed so that the divalent cations are adsorbed to the resin. The process may also include the step of MEG reclamation or MEG regeneration. A regeneration brine may be used to regenerate the spent cation exchange resin without removing it from the ion exchange bed. The regeneration brine may be comprised of distilled water produced during the MEG reclamation or MEG regeneration process. The regeneration brine may also be comprised of sodium chloride that is produced during the MEG reclamation process. After use, the regeneration brine may be disposed of as waste or recycled to the brine storage tank and re-used to regenerate the cation exchange resin.
- The objects of this invention are to (1) provide a more efficient process to remove divalent cations contained in a rich MEG feed stream before the stream enters a MEG reclamation or MEG regeneration process; (2) simplify the removal process by eliminating required conditions for time and temperature; (3) reduce the volume, footprint, and cost of the processing equipment typically required to remove divalent cations from the rich MEG feed stream; (4) provide a renewable or reusable bed for divalent cation removal; (5) provide a process for physical separation of the divalent cations from the rich MEG feed stream, thus eliminating the need for additional chemicals; and (6) facilitate the disposal of waste streams.
-
FIG. 1 presents an embodiment of a process for removing divalent cations from a rich MEG feed stream as part of a MEG reclamation process, practiced according to this invention. -
FIG. 2 presents an embodiment of a process for removing divalent cations from a rich MEG feed stream as part of a MEG regeneration process, practiced according to this invention. -
- 10 Divalent cation removal process
- 15 Rich MEG feed stream
- 20 Ion exchange bed
- 25 Rich MEG stream with the majority of divalent cations removed
- 30 Flash separator
- 35 Sodium chloride waste stream
- 40 Vaporized water and MEG stream
- 45 Distillation column
- 150 Lean MEG
- 55 Distilled water
- 60 Brine storage tank
- 65 Regeneration brine
- 70 Waste stream of sodium chloride and calcium chloride brine
- 80 Sodium chloride
- 85 Rich MEG feed stream
- 90 Rich MEG stream with the majority of divalent cations removed
- 95 Vaporized water
- An ion exchange process may be used to remove divalent cations from the rich MEG feed stream before the feed stream enters the MEG reclamation process, as shown in
FIG. 1 , or the MEG regeneration process, as shown inFIG. 2 . This ion exchange process is different than conventional water treatment because the rich MEG feed stream is more viscous than water and 25 interacts differently with the ion exchange resins. In addition, the ion exchange resins of the present invention are subject to higher concentrations of sodium and calcium than would generally be found in water treatment systems. - As shown in
FIG. 1 , a preferred embodiment of a divalentcation removal process 10A practiced according to this invention begins with the richMEG feed stream 15, which is a mixture of produced water and MEG. The richMEG feed stream 15 is routed to a divalent cation removal step comprised of dualion exchange beds 20 which contain a strong cation exchange resin in the sodium form and alternate between adsorption and regeneration phases. In the adsorption phase, the resin removes divalent cations from the richMEG feed stream 15 by adsorbing the divalent cations from the produced water and displacing the sodium cations. Although twoion exchange beds 20 are shown inFIG. 1 , the ion exchange process may use more than two beds or a single bed. - The rich MEG stream with the majority of divalent cations removed 25 then exits the
ion exchange beds 20 and flows to the MEG reclamation process. The MEG reclamation process begins in aflash separator 30, where the pressure is reduced in order to separate salts from the rich MEG and water. A sodiumchloride waste stream 35 exits the bottom end of theflash separator 30, while the vaporized water andMEG stream 40 exits the top end and flows to thedistillation column 45. Thedistillation column 45 uses partial condensation to separate the water and MEG components of the vaporized water andMEG stream 40.Lean MEG 50 exits the bottom end of thedistillation column 45 and distilledwater 55 is discharged from the top end of thedistillation column 45. After meeting necessary quality requirements, the distilledwater 55 may be discharged as waste or recycled to thebrine storage tank 60. - Regeneration of the
ion exchange beds 20 may be accomplished with water containing large amounts of a salt. In the embodiment described inFIG. 1 , the sodiumchloride waste stream 35 from theflash separator 30 is combined with distilledwater 55 from thedistillation column 45 in thebrine storage tank 60 to formregeneration brine 65. At the beginning of the regeneration process, one of theion exchange beds 20 is taken off-line by diverting the flow of the richMEG feed stream 15 from thatbed 20 to thealternate bed 20. A stream ofregeneration brine 65 from thebrine storage tank 60 is then routed through the off-lineion exchange bed 20 in a direction opposite that of the flow of the richMEG feed stream 15. Divalent cations that have been adsorbed to the cation exchange resins inside theion exchange bed 20 leave the resins and enter the stream ofregeneration brine 65, forming a waste stream of sodium chloride andcalcium chloride brine 70 that exits from the top of theion exchange bed 20. The waste stream of sodium chloride andcalcium chloride brine 70 can be disposed of as waste or re-used to regenerate theion exchange beds 20. - As shown in
FIG. 2 , an ion exchange process may also be used to regenerate MEG by removing divalent cations from the rich MEG feed stream. This process may be used in applications where the produced water is relatively free of salts and the purity standards for MEG are less stringent. However, the MEG may contain divalent cations at a concentration that would cause equipment and scaling issues. Removing these ions protects downstream equipment and extends the useful life of the MEG. - A preferred embodiment of a divalent
cation removal process 10B practiced according to this invention begins with a richMEG feed stream 85, which is routed to a divalent cation removal step. The divalent cation removal step is comprised of dualion exchange beds 20 which contain a strong cation exchange resin in the sodium form and alternate between adsorption and regeneration phases. In the adsorption phase, the resin removes divalent cations from thefeed stream 85 by adsorbing the divalent cations from the produced water and displacing the sodium cations. Although twoion exchange beds 20 are shown inFIG. 2 , the ion exchange process may use more than two beds or a single bed. - The rich MEG stream with the majority of divalent cations removed 90 then exits the
ion exchange beds 20 and flows to adistillation column 45, which separates the water from the lean MEG.Lean MEG 50 exits the bottom end of thedistillation column 45, while the vaporizedwater 95 exits the top end. After the vaporizedwater 95 cools, it may be discharged as waste or recycled to thebrine storage tank 60. - Regeneration of the
ion exchange beds 20 may be accomplished with water containing large amounts of a salt. In the embodiment described inFIG. 2 ,sodium chloride 80 from an external source is combined with thewater 95 from thedistillation column 45 in thebrine storage tank 60 to formregeneration brine 65. At the beginning of the regeneration process, one of theion exchange beds 20 is taken off-line by diverting the flow of the richMEG feed stream 85 from thatbed 20 to thealternate bed 20. A stream ofregeneration brine 65 from thebrine storage tank 60 is then routed through the off-lineion exchange bed 20 in a direction opposite that of the flow of thefeed stream 85. Divalent cations that have been adsorbed to the ion exchange resins inside theion exchange bed 20 leave the resins and enter the stream ofregeneration brine 65, forming a waste stream of sodium chloride andcalcium chloride brine 70 that exits from the top of theion exchange bed 20. The waste stream of sodium chloride andcalcium chloride brine 70 can be disposed of as waste or re-used to regenerate theion exchange beds 20. - The present invention allows the MEG to remain in service for a longer period of time before the concentration of divalent cations increases to a level that could cause scaling or corrosion of the equipment. Another advantage of the present invention is that distilled water, which is produced during MEG reclamation and MEG regeneration and conventionally managed as a waste material, is recycled to form regeneration brine. Sodium chloride produced during MEG reclamation can also be recycled to form regeneration brine. Another advantage is that the waste stream of sodium chloride and calcium chloride brine from regeneration of the ion exchange beds contains only the salts that were originally present in the produced water. As a result, this waste stream can be discharged, if the appropriate water quality standards are met, to the marine environment or an injection well. This waste stream may also be recycled through the regeneration process for the cation exchange resin in the ion exchange beds until the concentration of divalent cations increases to a level that impairs regeneration of the resin.
- While preferred embodiments of a system and process for removing divalent cations from a rich MEG feed stream have been described in detail, a person of ordinary skill in the art understands that certain changes can be made in the arrangement of process steps and type of components used in the system and process without departing from the scope of the following claims.
Claims (20)
1. A process for removing divalent cations from a feed stream containing water and monoethylene glycol (MEG), the process comprising:
passing the feed stream through an ion exchange bed containing a cation exchange resin, wherein the divalent cations are adsorbed by the cation exchange resin to form an effluent stream; and
passing the effluent stream from the ion exchange bed through a distillation column to yield MEG and distilled water.
2. The process of claim 1 , further comprising regenerating the cation exchange resin by passing a regeneration brine through the cation exchange resin.
3. The process of claim 2 , wherein the regeneration brine comprises water from the distillation column.
4. The process of claim 3 , wherein the regeneration brine is stored in a brine storage tank.
5. The process of claim 4 , wherein the feed stream is passed through the ion exchange bed in a first direction, and the regeneration brine is routed from the brine storage tank to the ion exchange bed in a second direction opposite from the first direction.
6. The process of claim 5 , wherein the regeneration brine is formed by mixing sodium chloride from an external source with the water from the distillation column.
7. The process of claim 6 , wherein the regeneration brine is re-used to regenerate the ion exchange bed.
8. A process for removing divalent cations from a feed stream containing water and monoethylene glycol (MEG), the process comprising:
passing the feed stream in a first direction through an ion exchange bed containing a cation exchange resin, wherein the divalent cations are adsorbed by the cation exchange resin to form an effluent stream;
passing the effluent stream from the ion exchange bed through a distillation column to yield MEG and distilled water; and
regenerating the cation exchange resin by passing a regeneration brine through the ion exchange bed in a second direction opposite from the first direction.
9. The process of claim 8 , wherein the regeneration brine is formed in a regeneration brine tank by mixing sodium chloride from an external source with water from the distillation column.
10. The process of claim 8 , wherein the regeneration brine is sourced from a regeneration brine tank and is re-used.
11. The process of claim 8 , wherein the regeneration brine comprises sodium chloride sourced from MEG reclamation and water from the distillation column.
12. The process of claim 8 , wherein the regenerating forms a waste stream containing only salts originally present in the feed stream.
13. The process of claim 12 , wherein the regeneration brine is formed using water obtained from the distillation column.
14. The process of claim 12 , wherein the waste stream is used as a regeneration brine.
15. The process of claim 8 , wherein vaporized water from the distillation column is cooled and routed to a regeneration brine tank, and sodium chloride is added to the regeneration brine tank to form the regeneration brine.
16. The process of claim 15 , wherein the sodium chloride is obtained from an external source.
17. The process of claim 15 , wherein the sodium chloride is obtained from a waste stream of the regeneration operation.
18. A process for removing divalent cations from a feed stream containing water and monoethylene glycol (MEG), the process comprising:
passing the feed stream in a first direction through an ion exchange bed containing a cation exchange resin, wherein the divalent cations are adsorbed by the cation exchange resin to form an effluent stream;
passing the effluent stream from the ion exchange bed through a distillation column to yield MEG and distilled water; and
regenerating the cation exchange resin by passing a regeneration brine, formed using water from the distillation column, from a regeneration brine tank through the ion exchange bed in a second direction opposite from the first direction.
19. The process of claim 18 , wherein sodium chloride obtained as a waste stream from the regeneration process is added to the regeneration brine tank to make the regeneration brine.
20. The process of claim 19 , wherein sodium chloride from an external source is also added to the regeneration brine tank to make the regeneration brine.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/661,599 US20200071250A1 (en) | 2012-08-24 | 2019-10-23 | Divalent cation removal from rich monoethylene glycol (meg) feed streams by ion exchange |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/593,734 US9433875B2 (en) | 2012-08-24 | 2012-08-24 | Divalent cation removal from rich monoethylene glycol (MEG) feed streams by ion exchange |
US15/254,125 US20170050908A1 (en) | 2012-08-24 | 2016-09-01 | Divalent Cation Removal From Rich Monoethylene Glycol (MEG) Feed Streams By Ion Exchange |
US16/661,599 US20200071250A1 (en) | 2012-08-24 | 2019-10-23 | Divalent cation removal from rich monoethylene glycol (meg) feed streams by ion exchange |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/254,125 Continuation US20170050908A1 (en) | 2012-08-24 | 2016-09-01 | Divalent Cation Removal From Rich Monoethylene Glycol (MEG) Feed Streams By Ion Exchange |
Publications (1)
Publication Number | Publication Date |
---|---|
US20200071250A1 true US20200071250A1 (en) | 2020-03-05 |
Family
ID=48949214
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/593,734 Expired - Fee Related US9433875B2 (en) | 2012-08-24 | 2012-08-24 | Divalent cation removal from rich monoethylene glycol (MEG) feed streams by ion exchange |
US15/254,125 Abandoned US20170050908A1 (en) | 2012-08-24 | 2016-09-01 | Divalent Cation Removal From Rich Monoethylene Glycol (MEG) Feed Streams By Ion Exchange |
US16/386,906 Abandoned US20190241493A1 (en) | 2012-08-24 | 2019-04-17 | Divalent cation removal from rich monoethylene glycol (meg) feed streams by ion exchange |
US16/661,599 Abandoned US20200071250A1 (en) | 2012-08-24 | 2019-10-23 | Divalent cation removal from rich monoethylene glycol (meg) feed streams by ion exchange |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/593,734 Expired - Fee Related US9433875B2 (en) | 2012-08-24 | 2012-08-24 | Divalent cation removal from rich monoethylene glycol (MEG) feed streams by ion exchange |
US15/254,125 Abandoned US20170050908A1 (en) | 2012-08-24 | 2016-09-01 | Divalent Cation Removal From Rich Monoethylene Glycol (MEG) Feed Streams By Ion Exchange |
US16/386,906 Abandoned US20190241493A1 (en) | 2012-08-24 | 2019-04-17 | Divalent cation removal from rich monoethylene glycol (meg) feed streams by ion exchange |
Country Status (7)
Country | Link |
---|---|
US (4) | US9433875B2 (en) |
EP (1) | EP2888021A1 (en) |
BR (1) | BR112015003860A2 (en) |
CA (1) | CA2880889A1 (en) |
MX (1) | MX2015002094A (en) |
MY (1) | MY166800A (en) |
WO (1) | WO2014031269A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9433875B2 (en) * | 2012-08-24 | 2016-09-06 | Cameron International Corporation | Divalent cation removal from rich monoethylene glycol (MEG) feed streams by ion exchange |
FR3024142B1 (en) * | 2014-07-25 | 2016-08-26 | Novasep Process | METHOD OF PURIFYING GLYCOL AS ANTI-HYDRATE AGENT |
KR102647868B1 (en) * | 2016-12-01 | 2024-03-15 | 한화오션 주식회사 | MEG recovery apparatus using hybrid process based on hollow fiber membrane filter |
CN108794302A (en) * | 2018-08-23 | 2018-11-13 | 西南石油大学 | A kind of desalination regeneration technology of saliferous ethylene glycol rich solution |
US10954179B1 (en) * | 2019-08-28 | 2021-03-23 | Cameron International Corporation | Method and apparatus for filtering heat transfer fluid from a monoethylene glycol stream |
US11325878B2 (en) | 2019-09-13 | 2022-05-10 | Cameron International Corporation | Removing organic acids in monoethylene glycol recovery |
US11976770B2 (en) * | 2020-09-29 | 2024-05-07 | Saudi Arabian Oil Company | Solid removal in glycol reclamation |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1668052C3 (en) | 1967-12-07 | 1975-01-30 | Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt | Process for purifying glycols |
IL32812A (en) * | 1968-08-17 | 1974-05-16 | Asahi Chemical Ind | Process for producing fresh water and concentrated brine from brine |
US3732320A (en) | 1969-11-18 | 1973-05-08 | Cities Service Co | Process for purifying ethylene glycol |
US4518396A (en) | 1983-03-01 | 1985-05-21 | Gas Conditioning Industries, Inc. | Method of dehydrating natural gas |
US5294305A (en) * | 1993-05-06 | 1994-03-15 | Mobile Process Technology, Inc. | Ethylene glycol recovery process |
FR2711650B1 (en) | 1993-10-29 | 1995-12-01 | Elf Aquitaine | Process for the purification of a glycolic solution based on one or more glycols and containing, in addition, water and, as impurities, salts and hydrocarbons. |
US5785857A (en) | 1996-04-30 | 1998-07-28 | Mobile Process Technology, Inc. | Mobile process for the recovery of spent heat transfer fluids |
DE59801187D1 (en) | 1997-06-20 | 2001-09-13 | Ruhrgas Ag | METHOD AND ARRANGEMENT FOR DRYING A GAS |
US6023003A (en) * | 1998-01-13 | 2000-02-08 | Reading & Bates Development Co. | Process and system for recovering glycol from glycol/brine streams |
US6242655B1 (en) | 2000-07-11 | 2001-06-05 | Scientific Design Company, Inc. | Glycol purification |
FR2846323B1 (en) * | 2002-10-28 | 2004-12-10 | Inst Francais Du Petrole | PROCESS FOR REGENERATING AN AQUEOUS SOLUTION OF GLYCOL CONTAINING SALTS |
EP2188237A4 (en) * | 2007-07-30 | 2014-10-15 | Cameron Int Corp | Removing solids in monoethylene glycol reclamation |
GB0813484D0 (en) * | 2008-07-24 | 2008-08-27 | Rolls Royce Plc | Gas turbine engine nacelle |
CN101773749B (en) | 2010-03-01 | 2012-08-22 | 新疆石油学院 | Method for purifying polyol for preventing natural gas from freezing and dehydrating natural gas and equipment |
US9433875B2 (en) * | 2012-08-24 | 2016-09-06 | Cameron International Corporation | Divalent cation removal from rich monoethylene glycol (MEG) feed streams by ion exchange |
US9089790B2 (en) * | 2012-08-24 | 2015-07-28 | Cameron International Corporation | Hydrocarbon and divalent cation removal from rich mono ethylene glycol (MEG) feed streams by regenerable filters |
US8808546B2 (en) * | 2012-08-24 | 2014-08-19 | Cameron International Corporation | Hydrocarbon removal from gas process feed streams by regenerable filters |
-
2012
- 2012-08-24 US US13/593,734 patent/US9433875B2/en not_active Expired - Fee Related
-
2013
- 2013-07-22 BR BR112015003860A patent/BR112015003860A2/en not_active IP Right Cessation
- 2013-07-22 WO PCT/US2013/051495 patent/WO2014031269A1/en active Application Filing
- 2013-07-22 CA CA2880889A patent/CA2880889A1/en not_active Abandoned
- 2013-07-22 MY MYPI2015000194A patent/MY166800A/en unknown
- 2013-07-22 EP EP13747546.3A patent/EP2888021A1/en not_active Withdrawn
- 2013-07-22 MX MX2015002094A patent/MX2015002094A/en unknown
-
2016
- 2016-09-01 US US15/254,125 patent/US20170050908A1/en not_active Abandoned
-
2019
- 2019-04-17 US US16/386,906 patent/US20190241493A1/en not_active Abandoned
- 2019-10-23 US US16/661,599 patent/US20200071250A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP2888021A1 (en) | 2015-07-01 |
US20140054160A1 (en) | 2014-02-27 |
WO2014031269A1 (en) | 2014-02-27 |
MX2015002094A (en) | 2015-05-11 |
BR112015003860A2 (en) | 2017-07-04 |
MY166800A (en) | 2018-07-23 |
CA2880889A1 (en) | 2014-02-27 |
US20190241493A1 (en) | 2019-08-08 |
US9433875B2 (en) | 2016-09-06 |
US20170050908A1 (en) | 2017-02-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20200071250A1 (en) | Divalent cation removal from rich monoethylene glycol (meg) feed streams by ion exchange | |
US9089790B2 (en) | Hydrocarbon and divalent cation removal from rich mono ethylene glycol (MEG) feed streams by regenerable filters | |
US20130193074A1 (en) | Water treatment process | |
EP2819953B1 (en) | Method of treatment of amine waste water and a system for accomplishing the same | |
US10124330B2 (en) | Method and apparatus for the removal of polyvalent cations from mono ethylene glycol | |
RU2724779C1 (en) | Method for integrated processing of produced water of oil fields | |
US20150166363A1 (en) | Methods and systems for water recovery | |
US20150119609A1 (en) | Carboxylic acid salt removal during hydrate inhibitor recovery | |
US10118123B2 (en) | Process for the removal of heat stable salts from acid gas absorbents | |
JP6640217B2 (en) | Method for recovering a processing liquid from a stream containing an alkaline earth metal salt | |
MX2015002256A (en) | Hydrocarbon removal from gas process feed streams by regenerable filters. | |
US20140326674A1 (en) | Zero Liquid Discharge Method for High Silica Solutions | |
JP2004358316A (en) | Method of treating fluorine-containing water, and device therefor | |
US20230023829A1 (en) | Method for regenerating an aqueous solution of meg containing salts with purge treatment | |
US20150021519A1 (en) | Method to remove carbonate from a caustic scrubber waste stream | |
KR101596324B1 (en) | Hybrid regeneration apparatus and method of liquid desiccant for gas dehydration process | |
NZ728433B2 (en) | Process for recovering processing liquids from streams containing alkaline earth metal salts | |
CA2873453A1 (en) | Zero liquid discharge method for high silica solutions | |
AU2013264823A1 (en) | Methods and systems for water recovery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |