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WO2024252360A1 - Élimination de mercure de charges d'eau produites - Google Patents

Élimination de mercure de charges d'eau produites Download PDF

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Publication number
WO2024252360A1
WO2024252360A1 PCT/IB2024/055607 IB2024055607W WO2024252360A1 WO 2024252360 A1 WO2024252360 A1 WO 2024252360A1 IB 2024055607 W IB2024055607 W IB 2024055607W WO 2024252360 A1 WO2024252360 A1 WO 2024252360A1
Authority
WO
WIPO (PCT)
Prior art keywords
mercury
process according
ionic liquid
organic salt
active organic
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/IB2024/055607
Other languages
English (en)
Inventor
Sharizal B Mohd Azam Shah WONG
TG M Uzaini B TG MAT
M Syamzari B RAFEEN
Safwan B A SALAM
John Holbrey
Emily Byrne
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.)
Petroliam Nasional Bhd Petronas
Original Assignee
Petroliam Nasional Bhd Petronas
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 Petroliam Nasional Bhd Petronas filed Critical Petroliam Nasional Bhd Petronas
Publication of WO2024252360A1 publication Critical patent/WO2024252360A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0446—Juxtaposition of mixers-settlers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0488—Flow sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4696—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrophoresis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature

Definitions

  • R a is preferably selected from Ci to C30, linear or branched, alkyl, more preferably C2 to C20 linear or branched alkyl, still more preferably, C2 to C10 linear or branched alkyl, and most preferably R a is selected from ethyl, n-butyl, n-hexyl and n-octyl.
  • the sulfur is preferably selected from elemental sulfur. It has been surprisingly found that significantly increased amounts of bulk mercury can be extracted from a mercury-containing produced waters feed when the sulfur source is selected from elemental sulfur.
  • Figure 2a illustrates sample vials containing five different ionic liquids
  • the gaseous feed formed (8) is then transferred to a mercury removal unit (MRU) (14) in order to further reduce the concentration of any mercury species remaining following treatment with the active organic salt composition (2).
  • the mercury removal units may comprise fixed bed adsorbents such as activated carbon, zeolite and alumina, through which the gaseous feed can flow, removing at least a portion of mercury present. In alternative embodiments, the presence of a MRU following treatment with the active organic salt composition will not be required.
  • the gaseous feed can be further treated to meet industry standards by undergoing dewatering (16) and acid gas removal treatments (18) to at least partially remove H2S and/or CO2 present.
  • the mixture of fuels may optionally be transferred to a further mercury removal unit (MRU) (22), if further reduction of mercury content is required.
  • MRU mercury removal unit
  • the treated condensate can then be separated (54) into hydrocarbon products for example using flash distillation or fractional distillation.
  • the stream collected from the bottom of the distillation tower is heavy naphtha fuel (56).
  • the separated naphtha fuel (56) may optionally be transferred to a further mercury removal unit (MRU) (58), if further reduction of mercury content is required, to produce a final naphtha fuel product (60).
  • MRU mercury removal unit
  • the reduced mercury naphtha formed may undergo additional refining/upgrading processes, including hydrotreating processes to reduce the amount of sulphur present, catalytic cracking and/or hydrocracking to reduce the presence of larger hydrocarbon compounds, and optionally blending with other streams (62), in order to produce a fuel meeting all of the requisite chemical, physical, economic and inventory requirements of the required hydrocarbon product.
  • the refined/upgraded product may further undergo treatment in a mercury removal unit (MRU) (64), if necessary.
  • MRU mercury removal unit
  • the hydrocarbon product may then be separated (66) into hydrocarbon products, for example using flash distillation or fractional distillation.
  • a desalter 68
  • small inorganic salts such as NaCI, CaCh and MgCh are removed from the crude oil by extraction into an aqueous phase.
  • wastewater from the produced water feed (46) may be used to remove inorganic salts from crude oil.
  • the treated crude oil may then be combined with the treated condensate and separated (54) into hydrocarbon products for example using flash distillation or fractional distillation .
  • the active organic salt composition may be contacted with the fluid feed directly prior to the feed entering the mercury removal unit. In this way, the occurrence of premature saturation of mercury adsorbents within the mercury removal units can be reduced.
  • FIG 3 clearly illustrates that each of the active organic salt compositions (PTA-1 +S to PTA-5+S) produce spectra comprising absorption bands around 470 nm and 615 nm, which correlates with earlier research. Without being bound by theory, it is believed that the slight shifts in the measured absorption peaks is due to the use of a different solvent (/.e. an ionic liquid) compared to the earlier research of Boros et al. 2010.
  • the effectiveness of three types of mercury extracting agent in particular aqueous Na2S, aqueous K2S, TMT15 (C 3 N 3 S 3 Na 3 ) (all known in the art) and active organic salt compositions in accordance with the present invention, were compared .
  • the mercury extracting agent in each example was added to an onshore produced waters in a mass ratio of 1 :1 with regards to the amount of mercury present within the produced water.
  • the selected produced waters feedstock comprised approximately 1000 pg/kg of [Hg(NO 3 )2],
  • the active organic salt compositions of the present invention that were analysed are provided in Table 2 below.
  • the sulfur source added in each example was elemental sulfur.
  • the samples were prepared by adding sulfur to the ionic liquid whilst stirring at 200 to 400 rpm until the concentration of sulfur in the ionic liquid reached 1000 ppb wt, and heating the mixture to up to 70°C until a dark-greenish blue mixture was obtained (the active salt composition).
  • the mercury extracting agent and onshore produced waters were combined before shaking for 15 to 20 seconds at room temperature (25 °C).
  • the shaking was then stopped, and the precipitated mercury salt separated from the produced waters and ionic liquid by centrifuging techniques.
  • the samples were centrifuged at 4,400 rpm for 15 to 20 minutes. This step was repeated three times. The majority of the produced water was then decanted from the centrifuged samples leaving only a small volume of produced water containing the precipitated mercury salt suspended therein. The suspension was then air dried to remove any remaining produced waters.
  • mercury is removed from the produced waters feed in the form of a mercury sulfide precipitate, preferably as beta-mercury (II) sulfide (metacinnabar).
  • the mercury salt precipitate formed may be at least partially separated from the produced waters product by filtration means (such as the use of a membrane or ceramic filter), centrifugation, cyclone or gravity separation. Accordingly, increasing the particle size of the p-HgS solids formed could facilitate the removal of these compounds from the reduced mercury produced waters feed.
  • the ionic liquid present in the active organic salt composition at least partially affects the volume mean particle size of the p- HgS precipitate produced.
  • the volume mean particle size of the -HgS precipitate varies from 8.26 pm (PTA-2+S) to 16.55 pm (PTA-1 +S).
  • PTA-2+S 8.26 pm
  • PTA-1 +S 16.55 pm
  • the present invention can be tailored to increase the particle size of the mercury precipitate formed and thereby facilitate the removal of mercury from a mercury-containing produced waters feed.
  • the present invention provides an improved method of extracting mercury from mercury-containing produced water feeds.
  • the defined active organic salt compositions are more adept at extracting mercury, the use of such compositions is more effective and reliable at producing produced water products which meet industry implemented regulations when the concentration of mercury in the feed varies.
  • the use of active organic salt compositions as defined herein further reduces the amount of mercury present in the treated produced water feed compared to other known extracting methods/agents, the requirement of multiple or repeated extraction steps in order to meet the required mercury concentration is avoided. In this way, use of organic salt compositions as defined herein provides a more time and cost-effective method of processing produced waters generated at oil and gas refineries.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé pour éliminer le mercure d'une charge d'eau produite, et plus spécifiquement par utilisation d'une composition de sel organique actif.
PCT/IB2024/055607 2023-06-07 2024-06-07 Élimination de mercure de charges d'eau produites Pending WO2024252360A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI2023003354 2023-06-07
MYPI2023003354 2023-06-07

Publications (1)

Publication Number Publication Date
WO2024252360A1 true WO2024252360A1 (fr) 2024-12-12

Family

ID=93795185

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2024/055607 Pending WO2024252360A1 (fr) 2023-06-07 2024-06-07 Élimination de mercure de charges d'eau produites

Country Status (1)

Country Link
WO (1) WO2024252360A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5082569A (en) * 1990-12-03 1992-01-21 Uop Removal of metals from liquefied hydrocarbons
US5989506A (en) * 1996-12-18 1999-11-23 Uop Llc Process for the removal and recovery of mercury from hydrocarbon streams
US20120121485A1 (en) * 2009-04-06 2012-05-17 Robin Don Rogers Process for removing metals from hydrocarbons
US20170037323A1 (en) * 2010-10-05 2017-02-09 The Queen's University Of Belfast Process for removing metals from hydrocarbons
US20180051216A1 (en) * 2015-03-03 2018-02-22 Petroliam Nasional Berhad (Petronas) Process for removing heavy metals from hydrocarbons

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5082569A (en) * 1990-12-03 1992-01-21 Uop Removal of metals from liquefied hydrocarbons
US5989506A (en) * 1996-12-18 1999-11-23 Uop Llc Process for the removal and recovery of mercury from hydrocarbon streams
US20120121485A1 (en) * 2009-04-06 2012-05-17 Robin Don Rogers Process for removing metals from hydrocarbons
US20170037323A1 (en) * 2010-10-05 2017-02-09 The Queen's University Of Belfast Process for removing metals from hydrocarbons
US20180051216A1 (en) * 2015-03-03 2018-02-22 Petroliam Nasional Berhad (Petronas) Process for removing heavy metals from hydrocarbons

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