US20150233003A1 - Method of hypochlorite production and related sea water electrolyzer with anti scale implemen - Google Patents

Method of hypochlorite production and related sea water electrolyzer with anti scale implemen Download PDF

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Publication number
US20150233003A1
US20150233003A1 US14/403,773 US201214403773A US2015233003A1 US 20150233003 A1 US20150233003 A1 US 20150233003A1 US 201214403773 A US201214403773 A US 201214403773A US 2015233003 A1 US2015233003 A1 US 2015233003A1
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electrolyzer
sea water
jets
water
gap spaces
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English (en)
Inventor
Luigi Righetti
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SESPI Srl
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Assigned to S.E.S.P.I. S.r.I. reassignment S.E.S.P.I. S.r.I. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RIGHETTI, Luigi
Publication of US20150233003A1 publication Critical patent/US20150233003A1/en
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    • 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
    • C02F1/4602—Treatment of water, waste water, or sewage by electrochemical methods for prevention or elimination of deposits
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • 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
    • C02F1/4604—Treatment of water, waste water, or sewage by electrochemical methods for desalination of seawater or brackish water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C25B1/265—Chlorates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B9/06—
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46119—Cleaning the electrodes
    • 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
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4611—Fluid flow
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention

Definitions

  • the present disclosure relates in general to electrolytic hypochlorite generation in diluted impure saline solutions like sea water and in particular to a method and implement for contrasting build up of scale over electrode and other surfaces inside the electrolyzer.
  • the electrolysis of sea water is commonly used for the direct production of hypochlorite to prevent bio-fouling and scaling of cooling systems, water ballasts, and alike.
  • Hypochlorite has a specific oxidizing and sterilizing effect and regenerates the original chloride ion when contacting organic substances or by effect of light, heat or of readily oxidizable ions, thus leaving no noxious residues in the sea water after the sterilization process.
  • Calcium, magnesium, iodine, bromine, sulfur and many heavy metals ions may be found.
  • calcium and magnesium are present in relatively large amounts in sea water and cause a severe scaling of the surface of the negatively biased electrodes and other surfaces. These scales are generally porous and do not interfere with the normal functioning of the cell, but their rapid growth makes them more and more compact and cause an increase of the operating cell voltage and consequent waste of electric power.
  • FIG. 1 A commonly preferred architecture of electrolyzer for an electro-chlorination plant is depicted in FIG. 1 .
  • a tubular casing contains a pack of spacingly interleaved planar anodes and cathodes defining interelectrodic gap spaces there between, practically composing a multiplicity of electrolytic cells, electrically parallelized (4 cells in parallel) in a tranverse direction and serialized (5 cells in series) in the longitudinal direction of the tubular casing of the electrolyzer, connected to a DC source through a positive connector and a negative connector at the opposite ends of the tubular casing.
  • the growth of scaling in the interelectrodic gap increasingly hinders a correct distribution of the flow of sea water between the flat counter-opposed surfaces of the metal plate electrodes as far as clogging definitely the electrode pack of the electrolyzer.
  • Each acid wash phase usually takes from 3 to 5 hours with associated loss of production besides the cost of the acid (commonly HCl), waste liquor treatment/disposal and hazard management costs.
  • the interval between these scheduled maintenance operations may be as short as 10-25 days.
  • Objective of the applicant was to find a viable way to alleviate the frequency and/or duration of the periodic down times of an electro-chlorination plant, required for carrying out an effective acid wash of the interior of the electrolyzer after a period of operation and to reduce acid consumption and the power costs associated to such unavoidable routine maintenance of the plant.
  • the idea has been to introduce into the stream of sea water pumped through the tubular casing of the electrolyzer a plurality of secondary or ancillary streams of highly pressurized water in form of high speed jets ejected from an array of nozzles, disposed at regular intervals along the whole length of at least one side of the elongated pack assembly.
  • the location of the many nozzles, their distance from the electrode pack and the spacing intervals among each other are such to ensure that high speed jets of liquid encroach (are directed toward) into the interelectrodic gap spaces, in a direction orthogonal or inclined in respect of the longitudinal flow direction of sea water there through; the sought effect being to disrupt a probably laminar flow of sea water within the interelectrodic gap spaces and induce an energetic turbulence of the liquid therein.
  • the overpressure of the liquid to be injected should be sufficient to produce energetic (high speed) jets adapted to encroach deep inside the interelectrodic gap spaces.
  • the kinetic energy of the jets is gradually absorbed by the liquid flowing through the gap spaces from the inlet end to the outlet end of the tubular casing of the electrolyzer containing the elongated electrode pack.
  • a periodic ejection of jets of pressurized liquid may be carried out during normal operation of the electrolyzer or the electrolysis process may be interrupted during the ejection phase.
  • interruption of the DC electrical powering of the electrodes and of the forced flow of the process liquid through the electrolyzer is commanded when the discharge valve of drain nozzles present along the bottom of the electrolyzer need to be opened for discharging accumulated scale, displaced by the jets from the electrode surfaces and sunk to the bottom.
  • the high pressure injection of orthogonal/inclined jets does not need to be continuous and that an intermittent injection is preferable.
  • the intermittent high pressure scale sweeping phase may have a duration of about 5 min. and be carried out every 15-30 minutes.
  • duration and frequency of the scale sweeping phase may be adjusted by a control PLC depending on operating conditions and quality of the processed saline water.
  • the PLC is also programmable for implementing scale sweeping phases without interruption of the electrochemical process and scale sweeping phases with simultaneous interruption of the electrochemical process and opening of the bottom discharge drains, according to needs or pre-established time schedules.
  • the pressure of the injected liquid may be comprised between 5 and 10 N/m2.
  • the ratio between the cumulative flow rate of liquid ejection through said plurality of nozzles and the flow rate of said forced flow of process liquid through the electrolyzer may be comprised between 0.2 and 0.6.
  • the cumulative flow rate of the plurality of secondary or ancillary streams of highly pressurized water in form of high speed jets practically amounts to a fraction of the flow rate of the main flow of sea water pumped through the electrolyzer. This limits the power requirement for pressurizing the liquid to be injected for a surprisingly low cost/benefit ratio when considering the overall economical figures of the electro-chlorination process.
  • FIG. 1 is a basic cross sectional view showing the structure of an electrolyzer commonly used for generating sodium hypochlorite in a stream of sea water or equivalent saline solution.
  • FIG. 2 is a photograph and an enlargement of it of the electrode pack of a commercial sea water electrolyzer, practically destroyed by an unchecked growth of scale.
  • FIGS. 3A , 3 B, 3 C and 3 D provide a basic illustration of an electrolyzer for sea water electrolysis embodying the novel anti scaling implement of this invention.
  • FIGS. 4A and 4B are a view from atop and an enlarged partial view, respectively, of the pre-assembled electrode pack of the electrolyzer.
  • FIG. 5 is an exploded detail view of a pressurized water distributor with uniformly spaced nozzle assembly according to an exemplary embodiment.
  • FIG. 6 is a general functional diagram of an electro-chlorination plant using the novel electrolyzer of this invention.
  • FIG. 3A , FIG. 3B , FIG. 3C and FIG. 3D are a longitudinal cross sectional view and end views without and with sectional views of the electrode pack ,off and in coincidence with one array of spacers, respectively, of an exemplary commercial sea water electrolyzer for electro-chlorination plants, equipped with the anti-scaling implements of this invention.
  • the electrolyzer has a tubular casing 1 , commonly a horizontal cylindrical shell of PVC with an outer cladding of GRP, closed by end flanges (not shown), adapted to contain a pre-assembled multi electrode pack (C1, . . . , A1), the functional arrangement of which already depicted in FIG. 1 , may be recognized in the view of the pack from atop of FIG. 4A and in the partial enlarged drawing of FIG. 4B , where the insulating spacers between the plate electrodes are more visible.
  • the tubular casing 1 has a sea water inlet nozzle 2 and an outlet nozzle 3 through which hypochlorite containing sea water and hydrogen bubbles dispersed in the liquid stream exit the electrolyzer.
  • the bottom nozzles 4 serve for flush discharging the acid solution with which the interior of the electrolyzer if filled when carrying out the periodic acid washings.
  • An optional nozzle 5 at the top may be provided, closed with a transparent pane, in order to provide a visual inspection window of the state of the scale accumulation.
  • the electrode pack assembly defines a multicell electrical series formed by planar titanium plate electrodes, 1 mm thick, each having, over the anodically polarized portion (A1, A2, A3, . . . , A7) of the plate, a non passivating, conductive metal oxide coating with a low chlorine ion oxidation overvoltage and without any coating or with a low hydrogen ion discharge overvoltage metallic coating over the cathodically polarized portion (C1, C2, C3, . . . , C7).
  • planar titanium plate electrodes 1 mm thick, each having, over the anodically polarized portion (A1, A2, A3, . . . , A7) of the plate, a non passivating, conductive metal oxide coating with a low chlorine ion oxidation overvoltage and without any coating or with a low hydrogen ion discharge overvoltage metallic coating over the cathodically polarized portion (C1, C2, C3, . . . , C7).
  • a terminal cathodic head (C1) and a terminal anodic head (A1) each generally in form of a about 17 to 65 teeth comb-like assembly of parallel cathode plates and anode plates, respectively, (refer also the basic functional scheme of FIG. 1 ) connect to a DC power source via rods (electrical connection leads) passing through closing end flanges of the tubular casing 1 .
  • the novel implements of this invention consists of two additional nozzles 6 t and 6 b, respectively at the top and at the bottom of the casing 1 , accommodating a flanged inlet pipe 7 t and 7 b, respectively, a threaded end of which tightens in a respective “T” coupling between the two portions 10 t (and the two portions 10 b ) of a top and a bottom distributor pipe of high pressure water, closed at both ends.
  • the distributor pipe may be in a single piece, one end of which passing through one of the end closing flanges of the tubular casing 1 for allowing a direct external hydraulic connection.
  • each distributor pipe has a plurality of equally spaced and similarly oriented nozzles 9 t and 9 b, respectively, adapted to release highly energetic jets (high exit velocity of the pressurized water) directed toward the spaced edges of the parallel electrode plates and the related interelectrodic gap spaces along which flows the stream of sea water pumped through the electrolyzer.
  • the electrode pack assembly had the following dimensions: length 274 cm, width 24,8 cm, height 16,6 cm; the distributors were of 3 ⁇ 4 A′′ PVC pipe and had 17 threaded PVC nozzles coupled to the pipe distributor at 150 mm intervals. The nozzles were set at a distance of 60 mm from the plane of the spaced edges of the parallel plate electrodes.
  • the preferred main construction material for piping, flanges internal and external supports, hydraulic seal fixtures and other fixtures is generally PVC, though other plastics may be alternatively used.
  • FIG. 6 is a simplified general functional diagram of an electro-chlorination plant embodying the novel implements of this invention.
  • the scheme and the legend of the symbolic representation of the functional element make the illustration perfectly legible by the skilled person and no specific description is deemed necessary for the fullest comprehension of the claimed invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US14/403,773 2012-05-28 2012-05-28 Method of hypochlorite production and related sea water electrolyzer with anti scale implemen Abandoned US20150233003A1 (en)

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PCT/IT2012/000155 WO2013179314A1 (en) 2012-05-28 2012-05-28 Method of hypochlorite production and related sea water electrolyzer with anti scale implement

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US (1) US20150233003A1 (zh)
EP (1) EP2691341B1 (zh)
JP (1) JP5828058B2 (zh)
KR (1) KR20150027140A (zh)
CN (1) CN104507874B (zh)
ES (1) ES2538662T3 (zh)
HK (1) HK1207057A1 (zh)
WO (1) WO2013179314A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019165161A1 (en) * 2018-02-22 2019-08-29 Evoqua Water Technologies Llc Electrochlorination system configurations for the generation of high product strength solutions
WO2021034201A1 (en) 2019-08-22 2021-02-25 National Oilwell Varco Norway As Cathode coating for an electrochemical cell
DE102020002642A1 (de) 2020-05-02 2021-11-04 Math Lemouré Verfahren zur Entsalzung von Meerwasser
EP4223704A1 (en) 2022-02-02 2023-08-09 Grant Prideco, Inc. Apparatus for cleaning seawater with improved electrochemical cell

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170009005A (ko) 2015-07-15 2017-01-25 대우조선해양 주식회사 자외선을 이용한 해수 인양 펌프의 해양생물증식 방지 장치 및 해수 인양 펌프의 해양생물증식을 방지하는 방법
CN106435641B (zh) * 2016-08-30 2018-02-09 江苏永冠给排水设备有限公司 一种集成式防结垢的次氯酸钠发生器装置及实现方法

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US4248690A (en) * 1980-01-28 1981-02-03 Pennwalt Corporation Apparatus for production of sodium hypochlorite
CH653376A5 (it) 1982-10-27 1985-12-31 Panclor Sa Produzione elettrolitica di ipoclorito da acqua di mare: metodo di pretrattamento dell'acqua di mare per migliorarne le caratteristiche chimico-fisiche.
US7048842B2 (en) * 2001-06-22 2006-05-23 The Procter & Gamble Company Electrolysis cell for generating chlorine dioxide
IL142984A0 (en) * 2001-05-06 2002-04-21 Scaletech Ltd Apparatus and method for preventing scale formation in circulating water systems
US7244348B2 (en) * 2004-11-29 2007-07-17 Severn Trent De Nora, Llc System and method for treatment of ballast water
WO2008062970A1 (en) * 2006-11-20 2008-05-29 Chi Jung Jeon Electro-chemical water processing apparatus and method thereof
KR100841664B1 (ko) * 2006-05-30 2008-06-26 전치중 전기화학적 수처리장치 및 수처리방법
KR100883444B1 (ko) * 2008-07-24 2009-02-17 (주) 테크윈 발라스트수 처리 장치 및 방법

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019165161A1 (en) * 2018-02-22 2019-08-29 Evoqua Water Technologies Llc Electrochlorination system configurations for the generation of high product strength solutions
US11814305B2 (en) 2018-02-22 2023-11-14 Evoqua Water Technologies Llc Electrochlorination system configurations for the generation of high product strength solutions
WO2021034201A1 (en) 2019-08-22 2021-02-25 National Oilwell Varco Norway As Cathode coating for an electrochemical cell
DE102020002642A1 (de) 2020-05-02 2021-11-04 Math Lemouré Verfahren zur Entsalzung von Meerwasser
EP4223704A1 (en) 2022-02-02 2023-08-09 Grant Prideco, Inc. Apparatus for cleaning seawater with improved electrochemical cell

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Publication number Publication date
KR20150027140A (ko) 2015-03-11
EP2691341B1 (en) 2015-03-04
EP2691341A1 (en) 2014-02-05
CN104507874A (zh) 2015-04-08
HK1207057A1 (zh) 2016-01-22
JP2015517910A (ja) 2015-06-25
CN104507874B (zh) 2016-10-12
ES2538662T3 (es) 2015-06-23
WO2013179314A1 (en) 2013-12-05
JP5828058B2 (ja) 2015-12-02

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