WO2013131102A1 - Générateur de déchets en produit sur site - Google Patents

Générateur de déchets en produit sur site Download PDF

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Publication number
WO2013131102A1
WO2013131102A1 PCT/US2013/028940 US2013028940W WO2013131102A1 WO 2013131102 A1 WO2013131102 A1 WO 2013131102A1 US 2013028940 W US2013028940 W US 2013028940W WO 2013131102 A1 WO2013131102 A1 WO 2013131102A1
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WO
WIPO (PCT)
Prior art keywords
electrolytic cell
waste stream
salinity
waste
water
Prior art date
Application number
PCT/US2013/028940
Other languages
English (en)
Inventor
Justin Sanchez
Craig Andrew BECKMAN
Thomas Edward MUILENBERG
Original Assignee
Miox Corporation
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 Miox Corporation filed Critical Miox Corporation
Publication of WO2013131102A1 publication Critical patent/WO2013131102A1/fr

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Classifications

    • 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
    • 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
    • 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
    • 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
    • C02F1/006—Water distributors either inside a treatment tank or directing the water to several treatment tanks; Water treatment plants incorporating these distributors, with or without chemical or biological tanks
    • 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
    • C02F2201/4612—Controlling or monitoring
    • 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
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46145—Fluid flow
    • 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
    • C02F2209/05—Conductivity or salinity
    • 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
    • C02F2209/05—Conductivity or salinity
    • C02F2209/055—Hardness
    • 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
    • C02F2209/40—Liquid flow rate
    • 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
    • C02F2303/14—Maintenance of water treatment installations

Definitions

  • the present invention relates to methods and apparatuses for electrolytic processing of waste brine solutions produced by water purification or other industrial processes, thereby producing one or more oxidants and/or disinfectants.
  • Electrolytic technologies utilizing dimensionally stable anodes have been developed to produce oxidant solutions from brine solutions, and these technologies have grown in market presence and interest across a variety of applications. Dimensionally stable anodes are described in U.S. Patent No.
  • Electrolytic cells have had wide use for the production of chlorine and mixed oxidants for the disinfection of water. Some of the simplest undivided electrolytic cells are described in U.S. Patent No. 4,761 ,208, entitled “Electrolytic Method and Cell for Sterilizing Water", and
  • An embodiment of the present invention is a method for producing an oxidant, the method comprising adjusting the salinity and/or hardness of a waste stream thereby forming a brine solution; and electrolyzing the brine solution to produce at least one oxidant.
  • the adjusting step preferably comprises measuring the salinity and/or hardness of the waste stream.
  • the adjusting step optionally comprises adding water or processed water to the waste stream to reduce the salinity of the waste stream and preferably further comprises varying the relative flow rates of the waste stream and the water or processed water being input into an electrolytic cell.
  • the adjusting step optionally comprises adding a saturated or near saturated salt solution to the waste stream to increase the salinity of the waste stream and preferably further comprises varying the relative flow rates of the waste stream and the saturated or near saturated salt solution being input into an electrolytic cell.
  • the adjusting step preferably comprises treating the waste stream by a method selected from the group consisting of softening, ion exchange, filtering, and reverse osmosis.
  • the brine solution preferably has a salinity between approximately 10 g/L and 40 g/L.
  • the adjusting step preferably reduces a cleaning frequency of the electrolytic cell.
  • Another embodiment of the present invention is a method for cleaning an electrolytic cell, the method comprising measuring a salinity and hardness of a waste stream to be electrolyzed, calculating a frequency for cleaning the electrolytic cell based on the measured salinity and hardness of the waste stream and a spacing between electrodes of the electrolytic cell, and cleaning the electrolytic cell in accordance with the calculated frequency.
  • the cleaning step preferably comprises reversing a polarity of the electrolytic cell and/or flushing solid contaminants from the electrolytic cell.
  • the flushing is preferably performed once or twice a day or after the electrolytic cell was cleaned by reversing the polarity of the electrolytic cell.
  • the method preferably further comprises adjusting the salinity and/or hardness of the waste stream, thereby reducing the cleaning frequency.
  • Another embodiment of the present invention is an electrolytic cell for electrolyzing a waste stream, the electrolytic cell comprising one or more devices for adjusting a flow rate of the waste stream entering an electrolytic cell; one or more dispersion tubes for transporting the waste stream into the electrolytic cell; a plurality of holes in the dispersion tubes, the holes angled to direct a flow of the waste stream toward bottom edges of the electrolytic cell; and one or more insulators
  • the additive stream may comprise water, processed water, a saturated salt solution, or a near saturated salt solution.
  • At least one of the devices can preferably flush the cell with the waste stream or water at a flushing flow velocity higher than (preferably at least twice) the operational flow velocity of the waste stream. Spacing between adjacent holes is preferably between approximately 0.5" and approximately 2".
  • the electrolytic cell preferably comprises electrodes which are spaced more widely than electrodes in an electrolytic cell designed to produce a similar quantity and strength of oxidants from a controlled brine stream.
  • the electrolytic cell preferably comprises intermediate electrodes, wherein spacing between adjacent intermediate electrodes is preferably between approximately 0.15" and approximately 0.5", and more preferably 0.25" +/- 0.1 ".
  • FIG. 1 is a schematic showing brine waste at a high salinity being converted electrochemically into usable oxidant.
  • FIG. 2 is a schematic showing brine waste at a low salinity being converted electrochemically into usable oxidant.
  • FIG. 3 is a schematic showing brine waste with a very high hardness to salinity ratio, where divalent cations are removed prior to electrolysis making the brine waste appropriate for electrolysis.
  • FIG. 4 is a high level schematic of an on-site electrolytic generator for converting brine waste to oxidant.
  • FIG. 5 is a cross section of an electrolytic cell for converting brine waste to oxidant.
  • FIG. 6 is a 3D representation of an electrolytic cell for converting brine waste to oxidant.
  • Embodiments of the present invention electrolize the waste stream from an industrial process, such as reverse osmosis, ion exchange softening, chemical softening, evaporation, distillation, produced or flowback water from oil and gas wells, to produce an oxidant and/or disinfectant.
  • This waste stream may be highly variable in salt content, presenting a unique challenge for consistent oxidant production.
  • a water source with low dissolved salt may be injected into the electrolyte for a high salinity waste stream at a rate determined by the operating current of the electrolytic cell. When the operating current is high, more water with low dissolved salt is preferably injected to reach the target operating current of the cell. Conversely, when the operating current is low, the water with low dissolved salts may be replaced with a concentrated brine solution injection to raise the current to the desired operating condition.
  • waste stream means an aqueous byproduct of an industrial process or application, including but not limited to frac water, produced water from oil and gas operations, cooling towers, desalination, or evaporation, the byproduct having a sodium chloride content of greater than approximately 1 g/L.
  • Embodiments of the present invention utilize an electrochemical process to convert a waste brine stream into a usable oxidant; one such process is shown in FIG. 1.
  • raw water 1 is first treated via softening process equipment 2 to remove divalent cations (typically those acknowledged as hardness) and other contaminants.
  • Softened waste water 3 is then put through purification processing equipment 4, such as reverse osmosis or other membrane processing equipment, to remove monovalent cations (i.e. salts) to create processed water 5 and brine waste 6.
  • Processed water 5 can often be used for industrial processes, is appropriate for discharge, and/or can even potentially be used as potable water.
  • Brine waste 6 is then processed and electrolyzed in on-site electrolytic generator 7 into oxidant 8.
  • Oxidant 8 can either be stored in a tank or directly used for a variety of applications (not shown).
  • dilution water 9 may optionally be used to dilute brine waste 6 in the on-site electrolytic generator if brine waste 6 is too salty.
  • Raw water 1 can be from virtually any source. However, certain sources have, or certain industrial processes produce a waste stream that has, a somewhat higher incidence of dissolved salts in the raw water, such as seawater, produced and/or flowback water from oil and gas operations, ground water, surface water, waste from industrial processes, waste water from municipalities, potable water, etc.
  • Brine waste 6 is often at a fairly high salinity, often greater than approximately 40 g/L but less than that for saturated brine (317 g/L).
  • dilution water 9 may be used to dilute the brine waste to a lower level that is more appropriate for electrolysis, typically between approximately 10 g/L and 40 g/L.
  • a small percentage of processed water 5 may optionally be used as the dilution water 9.
  • softening process equipment 2 may not be included in order to reduce cost and complexity of the system.
  • the purification processing equipment comprises or consists essentially of a simple filter to remove large particles (typically > 20 microns, but preferably > 100 microns) from brine waste 6.
  • FIG. 2 shows another embodiment of the invention.
  • solid brine storage tank 11 may be utilized.
  • solid salt is saturated in water, creating a brine solution 10 at or near saturation (approximately 317 g/L).
  • a small amount of saturated brine solution 10 is combined with the brine waste 6 for electrolysis by on-site electrolytic generator 7.
  • FIG. 3 Another embodiment of the invention is shown in FIG. 3.
  • divalent cations are removed from brine waste 6 using selective ion exchange process equipment 12, leaving a brine solution suitable for electrolytic generation of oxidant in on-site electrolytic generator 7.
  • FIG. 4 shows a high level schematic of an embodiment of on-site electrolytic generator 7.
  • the electrolytic generator takes brine waste 6 and either dilution water 9 or saturated brine solution 10 and generates oxidant 8 by electrolyzing it in electrolytic cell 14.
  • the relative flow rates of brine waste 6 and/or dilution water 9 or saturated brine solution 10 are preferably controlled by integrated controls 15, preferably via devices 13 such as pressure mechanisms, pumps, or valves. These input rates and the current and/or voltage applied to the electrolytic cell are preferably varied to maintain a controlled oxidant concentration.
  • devices 13 can be controlled to intermittently flush the electrolytic cell with very high flow rates (preferably greater than approximately two times the operational flow rate) of water or waste stream 6. If the latter is used, flushing can occur during the electrolysis process. This flushing prevents or reduces deposits from accumulating at the bottom of the electrolytic cell.
  • Integrated controls 15 also preferably control reversing the polarity of the cell, which removes deposits from the electrode surfaces. This process is more fully described in U.S. Patent Application Publication No. 20090229992.
  • electrolytic cell 14 is preferably designed such that it is robust and has an adequate lifetime.
  • FIG. 5 shows a cross section of an embodiment of a bipolar electrolytic cell useful for the current invention.
  • Primary electrodes 15 and intermediate electrodes 16 are preferably coated with Dimensionally Stable Anode (DSA) material, such as ruthenium, iridium, palladium, or other materials known in the art.
  • DSA Dimensionally Stable Anode
  • Both the primary anode and preferably cathode are coated with DSA so that the polarity of the cell can be intermittently reversed to remove any deposits on the electrodes.
  • a series of intermediate electrodes 16 are disposed between primary electrodes 15. The spacing from one electrode to the next is wider than on most typical electrolytic cells, preferably greater than 0.15" but less than approximately 0.5", preferably 0.25" +/- 0.1 ". In general, the wider the spacing the more inefficient the cell is, but wider spacing is useful with the present invention to prevent elevated contaminants from the incoming brine waste 6 from depositing on intermediate electrodes 16 and creating an electrical short circuit and arcing and/or premature cell failure.
  • Brine waste 6 is introduced to the electrolytic cell via dispersion tube 18, which comprises holes which direct the brine waste towards the bottom of electrolytic cell 14, and more preferably, to the bottom corners of the electrolytic cell 14.
  • the size, angles, and spacing of these holes down the length of the dispersion tube are preferably chosen to increase the velocity of the fluid, such that particles are less likely to settle into the bottom of the cell.
  • Electrolytic cell preferably comprises one or more electrical isolator blocks 17, which preferably extend from the bottom of the cell at least up to the bottom of the electrodes.
  • One isolator block is preferably present every few intermediate electrodes 16, which prevents loss of electrical efficiency and also protects the electrodes from being exposed to voltages beyond their breakdown voltages, for example due to high salinity of the brine waste.
  • electrical isolator blocks 17 are spaced every 5-10 electrodes, but depending on the chemistry desired in the oxidant and the salinity of brine waste 6, one electrical isolator block 17 could be present every 3 electrodes or even up to every 40 electrodes.
  • dispersion tubes 18 preferably distribute the brine waste 6 into the cell through an array of holes as described above. The holes are preferably spaced apart between approximately 0.5" and approximately 2", preferably 1 " +/- 0.25".
  • the characteristics of the brine waste vary considerably with different waste applications, which has implications on the frequency with which the electrolytic cell is cleaned.
  • the ratio of divalent cations to monovalent cations is particularly important.
  • the growth rate of contaminants on the electrodes is calculated, and for a given electrode spacing, the required cleaning frequency of the cell to prevent arcing between electrodes can be determined, after applying a given safety factor. From this cleaning frequency the expected life of an electrolytic cell can then be predicted given a certain number of cycles to failure.
  • treating the waste stream so that the salinity and/or hardness are in optimal ranges can greatly increase the lifetime of the cell by reducing required cleaning frequency.
  • the system can be optimized for energy conversion efficiency as salt is a waste product for various industrial processes and is therefore is extremely inexpensive.
  • a waste brine stream was created by a system very similar to the system shown in FIG.1 , in which the softening water processing equipment was an ion exchange resin softener, and the purification process equipment was a membrane based reverse osmosis filter.
  • the salinity of the waste brine stream was measured at 40 g/L, and had 100 grains/gallon hardness. Electrolyzing this waste brine stream was completed yielding an oxidant with 3400 mg/L FAC, with a required cell cleaning frequency of about 7 days corresponding to an expected cell life well over 10 years.
  • a waste brine stream consisting of produced water from an oil and gas operation was created by a system similar to the one shown in FIG.1 , with the exception that the softening water processing equipment was not present and the process equipment was a simple filter to remove particles > 80 microns.
  • the salinity of the waste brine stream was 17 g/L, and the hardness was 24 grains, and electrolyzing it yielded an oxidant with 2200 mg/L FAC, with a cell cleaning frequency of 12 days and an expected cell life well over 10 years.
  • a waste brine stream from a desalination plant was created with a system similar to the one depicted in FIG.1 , with no softening processing equipment.
  • the desalination plant relied on reverse osmosis to process the water.
  • the waste brine stream had a salinity of 210 g/L (typically too salty for effective electrolysis) and a hardness of 2800 grains/gallon.
  • the waste brine stream was recombined with a side stream of RO permeate as described herein to deliver a salinity of approximately 15 g/L to the electrolytic cell. Electrolysis of this stream yielded an oxidant with 4200 mg/L FAC, with a cell cleaning frequency of 1.3 days and an expected cell life of 3.9 years.
  • Waste blowdown from a cooling tower had approximately 4 g/L salt and a hardness of 180 grains/gallon. This waste blowdown was directly electrolyzied, yielding an oxidant with 650 mg/L

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un procédé et un appareil pour ajuster la salinité et/ou la dureté d'un flux de déchets de traitement de sorte que le flux puisse être électrolysé afin de former un oxydant ou un désinfectant. Est également prévue une cellule électrolytique présentant certaines caractéristiques telles que des électrodes largement espacées, des capacités de purge et des séparateurs isolants qui peuvent accueillir des flux de déchets qui ont une salinité, une dureté et une teneur en solides dissous qui diffèrent.
PCT/US2013/028940 2012-03-02 2013-03-04 Générateur de déchets en produit sur site WO2013131102A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261605929P 2012-03-02 2012-03-02
US61/605,929 2012-03-02

Publications (1)

Publication Number Publication Date
WO2013131102A1 true WO2013131102A1 (fr) 2013-09-06

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WO (1) WO2013131102A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201101717D0 (en) 2011-02-01 2011-03-16 Ide Technologies Ltd Chemical free and energy efficient desalination system
KR102208817B1 (ko) * 2014-03-28 2021-01-28 삼성전자주식회사 연수 장치
CN105174561A (zh) * 2015-09-10 2015-12-23 陕西省石油化工研究设计院 一种难生物降解高盐浓水处理工艺

Citations (5)

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US20030042134A1 (en) * 2001-06-22 2003-03-06 The Procter & Gamble Company High efficiency electrolysis cell for generating oxidants in solutions
US6610249B1 (en) * 1997-10-23 2003-08-26 Radical Waters Ip (Pty) Ltd Aqueous solution for disinfecting an animal product, a method and a plant for such disinfection
US20100206744A1 (en) * 2007-08-23 2010-08-19 Celio Lume Pereira Brine purification
US20110024122A1 (en) * 2008-03-12 2011-02-03 M-I Drilling Fluids Uk Limited Methods and systems of treating a wellbore
US20120048741A1 (en) * 2006-11-28 2012-03-01 Miox Corporation Electrolytic On-Site Generator

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DE2850575A1 (de) * 1978-11-22 1980-06-04 Metallgesellschaft Ag Verfahren zur elektrolytischen gewinnung von chlorsauerstoffsaeuren bzw. deren salze
KR100227969B1 (ko) * 1994-10-20 1999-11-01 사카모토 시게토시 전해수 생성장치
DE102005004063A1 (de) * 2005-01-21 2006-07-27 Alfred Kärcher Gmbh & Co. Kg Verfahren und Vorrichtung zur Herstellung einer Alkalimetallhypochloritlösung
US20070007146A1 (en) * 2005-07-07 2007-01-11 Severn Trent Water Purification, Inc. Process for producing hypochlorite
AU2010207883A1 (en) * 2009-01-29 2011-08-18 Astral Pool Australia Pty Ltd Electrolytic chlorinator

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Publication number Priority date Publication date Assignee Title
US6610249B1 (en) * 1997-10-23 2003-08-26 Radical Waters Ip (Pty) Ltd Aqueous solution for disinfecting an animal product, a method and a plant for such disinfection
US20030042134A1 (en) * 2001-06-22 2003-03-06 The Procter & Gamble Company High efficiency electrolysis cell for generating oxidants in solutions
US20120048741A1 (en) * 2006-11-28 2012-03-01 Miox Corporation Electrolytic On-Site Generator
US20100206744A1 (en) * 2007-08-23 2010-08-19 Celio Lume Pereira Brine purification
US20110024122A1 (en) * 2008-03-12 2011-02-03 M-I Drilling Fluids Uk Limited Methods and systems of treating a wellbore

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