WO2008079362A1 - Systèmes et procédés pour le traitement d'un flux de traitement - Google Patents

Systèmes et procédés pour le traitement d'un flux de traitement Download PDF

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Publication number
WO2008079362A1
WO2008079362A1 PCT/US2007/026219 US2007026219W WO2008079362A1 WO 2008079362 A1 WO2008079362 A1 WO 2008079362A1 US 2007026219 W US2007026219 W US 2007026219W WO 2008079362 A1 WO2008079362 A1 WO 2008079362A1
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WIPO (PCT)
Prior art keywords
unit
oxidation
stream
caustic
demineralization
Prior art date
Application number
PCT/US2007/026219
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English (en)
Inventor
Michael Howdeshell
Clayton B. Maugans
Chad L. Felch
Evgeniya Freydina
Li-Shiang Liang
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Siemens Water Technologies Corp.
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Application filed by Siemens Water Technologies Corp. filed Critical Siemens Water Technologies Corp.
Priority to US12/520,001 priority Critical patent/US20130008858A1/en
Priority to JP2009542950A priority patent/JP2010530793A/ja
Publication of WO2008079362A1 publication Critical patent/WO2008079362A1/fr

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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
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/06—Treatment of sludge; Devices therefor by oxidation
    • C02F11/08—Wet air oxidation
    • C02F11/086—Wet air oxidation in the supercritical state
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • 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
    • C02F2209/003—Downstream control, i.e. outlet monitoring, e.g. to check the treating agents, such as halogens or ozone, leaving the process
    • 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
    • C02F2303/02—Odour removal or prevention of malodour

Definitions

  • the present invention relates generally to process stream treatment and, more particularly, to systems and methods for the demineralization thereof.
  • Oxidation is a well-known technology for treating process streams, and is widely used, for example, to destroy pollutants in wastewater.
  • Wet oxidation for example, involves aqueous phase oxidation of undesirable constituents by an oxidizing agent, generally molecular oxygen from an oxygen-containing gas, at elevated temperatures and pressures.
  • the process can convert organic contaminants to carbon dioxide, water and biodegradable short chain organic acids, such as acetic acid.
  • Inorganic constituents including sulfides and mercaptides can also be oxidized; cyanides can be hydrolized.
  • wet oxidation may be used in a wide variety of applications to treat process streams, such as for subsequent discharge.
  • CEDI continuous electrodeionization
  • CEDI feeds are typically reverse osmosis treated streams.
  • the CEDI feed and product streams have low conductivities and therefore the cells are usually filled with a resin in order to increase conductivity of the matrix.
  • the cells are arranged in alternating pairs, with each pair generally producing one ultrapure water stream and one brackish reject stream.
  • the capacity of a CEDI module is dictated by how many cell pairs are included between the electrodes at the ends of the module. Typically, around 30-120 cell pairs are used per module for a commercial scale application.
  • the housing of the CEDI module is configured with ducting that collects the product water in one stream and the ionic reject stream in another. Commercial applications are typically in the range of 10 amps or less.
  • aspects relate generally to systems and methods for process stream treatment.
  • a system for treating an aqueous feed comprises an oxidation unit fluidly connected to a source of the aqueous feed, and a demineralization unit fluidly connected downstream of the oxidation unit, constructed and arranged to convert a product of the oxidation unit to a target compound.
  • a system for treating an aqueous feed containing a spent caustic comprises an oxidation unit fluidly connected to a source of the aqueous feed, and an electrochemical deionization unit fluidly connected downstream of the oxidation unit, constructed and arranged to generate a fresh caustic.
  • a method of treating an aqueous stream comprises oxidizing the aqueous stream to form an oxidation product, and converting the oxidation product to form a caustic stream.
  • FIG. 1 illustrates a treatment system in accordance with one or more embodiments
  • FIG. 2 illustrates a caustic stream treatment system in accordance with one or more embodiments
  • FIG. 3 illustrates operation of a continuous electrodeionization unit in accordance with one or more embodiments
  • FIGS. 4A-4E illustrate various system plumbing configurations as discussed in an accompanying Example
  • FIGS. 5 A and 5B present tables summarizing test conditions and results as discussed in an accompanying Example
  • FIGS. 6A-6E present CEDI module power charts as discussed in an accompanying Example
  • FIGS. 7A and 7B present data relating to effect of electrical current as discussed in an accompanying Example
  • FIGS. 8A-8D present mass balances for several different system configurations in accordance with one or more embodiments.
  • FIG. 9 illustrates determined strength of NaOH in CEDI product stream necessary to satisfy mass balance needs in accordance with one or more embodiments.
  • One or more embodiments relates generally to the treatment of process streams.
  • the systems and methods may be generally effective in treating process streams contaminated with one or more readily oxidizable compounds.
  • the systems and methods described herein may be implemented in a wide variety of applications in which it may be desirable to demineralize a process stream to facilitate downstream processing and/or to generate a product, such as a mineral stream.
  • some embodiments may be particularly useful in reducing an amount of new, fresh or make-up reactant needed to be supplied to an upstream industrial application.
  • certain embodiments may treat a spent caustic feed to form a fresh caustic stream, such as a sodium hydroxide stream, of sufficient strength and quality to be returned to an upstream ethylene production facility or petroleum refinery for use as a reactant.
  • Systems and methods may also be useful in producing a system effluent with an adjusted pH level relative to that of the initial process stream such that less pH correction, for example via chemical addition, is required for neutralization prior to discharge.
  • Embodiments may also make efficient use of equipment, such as both oxidation and demineralization treatment units, recognizing synergy therebetween to provide substantial advantages to both equipment suppliers and end users.
  • a system may be fluidly connected to a source of a process stream to be treated.
  • the process stream may be any process stream generally deliverable to the system for treatment.
  • the process stream may be an aqueous feed.
  • the process stream may be a wastewater stream.
  • the process stream may be moved through the system by an operation upstream or downstream of the system.
  • a source of an aqueous mixture to be treated by the system such as a slurry or other feed, may take the form of direct piping from a plant or intermediate holding vessel. After treatment, the process stream may be returned to an upstream process or may exit the system as waste.
  • the disclosed systems may receive process streams from community, industrial or residential sources.
  • process streams may originate, for example, from food processing plants, chemical processing facilities, gasification projects, or pulp and paper plants.
  • the process stream may be an aqueous feed from a process generally relating to polyolephins, such as an ethylene plant operation, or a petroleum refinery.
  • the aqueous feed may be a spent caustic feed in some embodiments.
  • the process stream may contain dissolved solids, such as minerals.
  • the minerals may have a value as a product stream if they can be separated or converted, as discussed in greater detail below.
  • minerals can be considered contaminants, making the process stream unsatisfactory for usage, treatment or disposal. Thus, it may be desirable to demineralize the process stream to extract a product and/or to ease downstream processing.
  • Various other components may be present in the process stream including, for example only, chloride, sodium hydroxide, sodium carbonate, total organic carbon (TOC) and iron.
  • a process stream may contain one or more target ions. Isolation and conversion of the target ions may be desirable as discussed herein.
  • the target ions in the process stream may be manipulated by the system to form a product stream of value or otherwise desirable.
  • the target ions may be present in the process stream as reactant byproducts due to upstream consumption of a consumable or reactant.
  • the system may isolate target ions and use them to form or generate a target compound.
  • the target ions present in the process stream may be precursors of a target compound.
  • the target compound to be generated may be the original consumable or reactant which gave rise to the target ion in the process stream upstream of the system.
  • the target compound may then be supplied upstream of the system for reuse.
  • the target compound may be a caustic compound, such as sodium hydroxide or ammonium sulfate.
  • Systems and methods may generally result in a product stream containing the target compound.
  • the process stream may be a spent caustic stream from an industrial caustic tower, or MEROX® type treatment process, such as one used in a petroleum refinery or ethylene production facility.
  • the spent caustic stream may typically include one or more reaction byproducts due to the consumption of fresh caustic in the caustic tower.
  • a reaction byproduct may generally include a target ion.
  • sodium sulfide as a reaction byproduct may include targeted sodium ions of interest.
  • the target ion may then be converted to form a target compound by the system.
  • sodium target ions may be converted to form a sodium hydroxide target compound.
  • the system may output a product stream containing sodium hydroxide in solution.
  • the spent caustic stream to be treated may also include other compounds, including any residual fresh caustic. It may be desirable to generate a fresh caustic stream from the spent caustic stream for delivery back to the caustic tower.
  • the process stream to be treated typically includes at least one undesirable constituent.
  • the undesirable constituent may be any material or compound targeted to be removed from the aqueous mixture, such as for public health, process design and/or aesthetic considerations.
  • an undesirable constituent may be toxic.
  • an undesirable constituent may tend to interfere with downstream operations, such as with membranes of a downstream separation or ion recovery unit.
  • an undesirable constituent may be generally characterized as contributing to a high chemical oxygen demand (COD) level of the process stream which may have negative consequences.
  • COD chemical oxygen demand
  • an undesirable constituent in the process stream is generally capable of being oxidized.
  • the undesirable constituents capable of being oxidized are organic compounds.
  • Certain inorganic constituents for example, sulfides, mercaptides and cyanides can also be oxidized.
  • sodium sulfide may be present in the process stream.
  • sodium sulfide may be present at a concentration of up to at least about 25,000ppm as S.
  • a treatment system may include a first treatment unit.
  • the first treatment unit may generally act upon the process stream to facilitate further processing thereof.
  • the first treatment unit may be effective in disrupting one or more specific chemical bonds in an undesirable constituent or degradation product(s) thereof.
  • the first treatment unit may generally treat oxidizable contaminants, such as those contributing to COD which may hamper the effectiveness, longevity and/or appropriateness of a downstream treatment, such as a demineralization step.
  • the first treatment unit may reduce the concentration or alter the nature of one or more undesirable constituents, such as by removing or stabilizing COD.
  • the first treatment unit may destroy or remove organic and reduced sulfur contaminants.
  • the first treatment unit may also generally put at least one target ion in a different or preferred form for downstream extraction as discussed herein.
  • the first treatment unit may generally be included as a pretreatment step prior to a demineralization step as discussed in greater detail below.
  • the first treatment unit or stage may be an oxidation unit.
  • An oxidation reaction is one destruction technique, capable of converting oxidizable organic contaminants to carbon dioxide, water and biodegradable short chain organic acids, such as acetic acid.
  • One aspect of the present invention involves systems and methods for oxidative treatment of aqueous mixtures containing one or more undesirable constituents.
  • An oxidation unit may oxidize sulfides to form nontoxic sulfate ions and oxidize other species also present in the process stream, such as a spent caustic stream.
  • Mercaptans may be rendered substantially innocuous, and COD contaminants may be converted into stable compounds which are less detrimental to downstream operations. Because 100% oxidation may not be achieved, some undesirable constituents may still be present in an oxidation product of the oxidation unit. Residual target compounds, such as sodium hydroxide and sodium carbonate, may also be present in the oxidation product.
  • typical oxidation products may include sodium carbonate and sodium sulfate.
  • Mineralized products may be formed, such as sulfate and carbonate ions.
  • At least one salt of a target ion such as sodium
  • a target ion such as sodium
  • sodium may form salt complexes with oxidized ions.
  • an oxidation product may include target ions, such as sodium, present in a different form than in the original process stream.
  • target ions such as sodium
  • sodium may generally be present as sodium sulfide upstream of the oxidation unit, but may exit the oxidation unit in sodium sulfate and/or sodium carbonate.
  • any oxidizer may be used in the oxidation unit.
  • any source of oxygen such as oxygen gas, ozone, peroxide and permanganate, or combinations thereof may be used.
  • any oxidation technique or technology, or combination thereof may be used.
  • photo-oxidation techniques may be used in which conversion of a reduced molecule to an oxidized form in the presence of oxygen is generally conducted via a set of chemical reactions that are initiated by photolysis.
  • UV or visible light may be employed.
  • the oxidation unit may generally be a liquid phase oxidation unit.
  • the liquid phase oxidation unit may be a wet oxidation unit, such as a wet air oxidation, wet peroxide oxidation or supercritical water oxidation unit.
  • a wet oxidation unit such as a wet air oxidation, wet peroxide oxidation or supercritical water oxidation unit.
  • an aqueous mixture or process stream including at least one undesirable constituent is wet oxidized.
  • the aqueous mixture is oxidized with an oxidizing agent at an elevated temperature and superatmospheric pressure for a duration sufficient to treat the at least one undesirable constituent.
  • Non-limiting embodiments involve process temperatures above about 150 0 C. More specifically, the process temperature may be above about 200 0 C. In some embodiments, the process temperature may be above about 250 0 C.
  • the duration or residence time may vary.
  • residence times may vary from about one-half hour up to ten hours. Some non-limiting embodiments involve residence times of about one hour, but shorter or longer residence time may be employed depending on conditions of an intended application.
  • the oxidation reaction may substantially destroy the integrity of one or more chemical bonds in the undesirable constituent. As used herein, the phrase "substantially destroy” is defined as at least about 95% destruction.
  • the process of the present invention is generally applicable to the treatment of any undesirable constituent capable of being oxidized.
  • the disclosed wet oxidation processes may be performed in any known batch or continuous wet oxidation unit suitable for the compounds to be oxidized.
  • aqueous phase oxidation is performed in a continuous flow wet oxidation system.
  • Any oxidizing agent may be used.
  • the oxidant is usually an oxygen-containing gas, such as air, oxygen-enriched air, or essentially pure oxygen.
  • oxygen- enriched air is defined as air having an oxygen content greater than about 21%.
  • an aqueous mixture from a source flows through a conduit to a high pressure pump which pressurizes the aqueous mixture.
  • the aqueous mixture is mixed with a pressurized oxygen-containing gas, supplied by a compressor, within a conduit.
  • the aqueous mixture flows through a heat exchanger where it is heated to a temperature which may initiate the oxidation.
  • the heated feed mixture then enters a reactor vessel at an inlet.
  • the wet oxidation reactions are generally exothermic and the heat of reaction generated in the reactor may further raise the temperature of the mixture to a desired value.
  • the bulk of the oxidation reaction occurs within the reactor vessel which provides a residence time sufficient to achieve the desired degree of oxidation.
  • the oxidized aqueous mixture and oxygen depleted gas mixture then pass from the reactor to a heat exchanger.
  • the hot oxidized effluent traverses the heat exchanger where it is cooled against incoming raw aqueous mixture and gas mixture.
  • the cooled effluent mixture flows through a conduit controlled by a pressure control valve and into a separator vessel where liquid and gases are separated.
  • the liquid effluent exits the separator vessel through a lower conduit while off gases are vented through an upper conduit.
  • Treatment of the off-gas may be required in a downstream off gas treatment unit depending on its composition and the requirements for discharge to the atmosphere.
  • the wet oxidized effluent may typically be discharged into a treatment plant, such as a biological or chemical treatment plant for polishing before discharge.
  • the effluent may also be recycled for further processing by the wet oxidation system.
  • the effluent may also be directed to a second unit operation, such as a demineralization or ion recovery unit as discussed more fully herein.
  • Sufficient oxygen-containing gas is typically supplied to the system to maintain residual oxygen in the wet oxidation system off gas, and the superatmospheric gas pressure is typically sufficient to maintain water in the liquid phase at the selected oxidation temperature.
  • the minimum system pressure at about 240 0 C is about 33 atmospheres
  • the minimum pressure at about 280 0 C is about 64 atmospheres
  • the minimum pressure at about 373°C is about 215 atmospheres.
  • the aqueous mixture is oxidized at a pressure of about 30 atmospheres to about 275 atmospheres.
  • the wet oxidation process may be operated at an elevated temperature below about 374 0 C, the critical temperature of water. In some embodiments, the wet oxidation process may be operated at a supercritical elevated temperature.
  • the retention time for the aqueous mixture within the reaction chamber should be generally sufficient to achieve the desired degree of oxidation. In some embodiments, the retention time is above about one hour and up to about eight hours. In at least one embodiment, the retention time is at least about 15 minutes and up to about six hours. In one embodiment, the aqueous mixture is oxidized for about 15 minutes to about four hours. In another embodiment, the aqueous mixture is oxidized for about 30 minutes to about three hours.
  • the wet oxidation process may be a catalytic wet oxidation process.
  • the oxidation reaction in the oxidation unit may generally be mediated by a catalyst.
  • the aqueous mixture containing at least one undesirable constituent to be treated is generally contacted with a catalyst and an oxidizing agent at an elevated temperature and superatmospheric pressure.
  • An effective amount of catalyst may be generally sufficient to increase reaction rates and/or improve the overall destruction removal efficiency of the system, including enhanced reduction of COD and/or TOC.
  • the catalyst may also serve to lower the overall energy requirements of the wet oxidation system.
  • Catalytic wet oxidation has emerged as an effective enhancement to traditional non-catalytic wet oxidation.
  • Catalytic wet oxidation processes generally allow for greater destruction to be achieved at a lower temperature and pressure, and therefore a lower capital cost.
  • An aqueous stream to be treated is mixed with an oxidizing agent and contacted with a catalyst at elevated temperatures and pressures.
  • Heterogeneous catalysts typically reside on a bed over which the aqueous mixture is passed, or in the form of solid particulate which is blended with the aqueous mixture prior to oxidation.
  • the catalyst may be filtered out of the oxidation effluent downstream of the wet oxidation unit for reuse.
  • the catalyst may be any transition metal of groups V, VI, VII and VIII of the Periodic Table.
  • the catalyst may be V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ag, or alloys or mixtures thereof.
  • the transition metal may be elemental or present in a compound, such as a metal salt.
  • the transition metal catalyst is vanadium.
  • the transition metal catalyst is iron.
  • the transition metal catalyst is copper.
  • a catalyst may be added to the aqueous mixture at any point in the wet oxidation system.
  • the catalyst may be mixed with the aqueous mixture.
  • the catalyst may be added to the source of the aqueous mixture feeding the wet oxidation unit, which catalyst source is fluidly connected to a storage tank.
  • the catalyst may be directly added to the wet oxidation unit.
  • the catalyst may also be supplied to the aqueous mixture prior to heating and/or pressurization.
  • the first treatment unit may generally produce a product stream, such as an oxidation product stream.
  • the oxidation unit may convert a process stream to an oxidation product stream.
  • the oxidation product stream may generally be suitable for further processing, such as in an ion recovery or demineralization unit as discussed herein.
  • the oxidation product may generally be substantially free of undesirable constituents.
  • the oxidation product may also contain one or more target ions from the original process stream which may be subject to further manipulation as discussed herein to generate a desired product.
  • a second treatment unit may be fluidly connected downstream of the first treatment unit. The second treatment unit may be configured to receive the oxidation product or oxidation product stream for further treatment.
  • the second treatment unit may generally convert an oxidation product of the first treatment unit to form a target compound or target stream.
  • the target compound may be generally isolated by the system for extraction, and may have value as a product stream or its removal may facilitate downstream operation.
  • the second treatment unit may generally demineralize the oxidation product stream to facilitate downstream treatment and/or produce a product stream rich in valuable minerals.
  • the second treatment unit may involve any technology generally capable of extracting ions to produce an ion-rich product stream as well as a stream with decreased mineral content.
  • the second treatment unit may be effective in conducting ion recovery of compounds including sodium, potassium, calcium, carbonate and sulfate.
  • a demineralization unit may, for example, include at least one ion exchange resin bed.
  • Ion exchange may generally involve the interchange of ions between a solution and a solid, commonly a resin, for demineralization. More specifically, ion exchange may involve reversible exchange of ions adsorbed on a mineral or synthetic polymer surface with ions in solution in contact with the surface. Target ions may be removed and replace with other ions, such as hydrogen ions. Target ions are then recovered from the exchange bed by passing water or other regeneration fluid through the bed periodically to replenish the resin with fresh hydrogen ions and produce a rinse water that contains a target compound, such as a sodium hydroxide stream.
  • a target compound such as a sodium hydroxide stream.
  • a cationic monomer may be polymerized within the structure of an anion-exchange resin, or vice versa, resulting in a polyelectrolyte structure. Regenerated, this structure may have its cationic groups in hydrogen form, and anionic groups in hydroxyl. Introduction of an electrolyte will displace the hydrogen and hydroxyl ions, causing their neutralization, saturating the resin with ionic species. Regeneration with water may cause the resin groups to hydrolyze, during which the target ion will be liberated and recovered. A lime solution may also be used to regenerate the bed to produce a target compound, such as sodium hydroxide.
  • a target compound such as sodium hydroxide.
  • concentrating or separation operations may also be employed to effect ion recovery or demineralization.
  • Distillation generally involves evaporation and subsequent condensation to collect vapors.
  • Crystallization and filtration processes such as nanofiltration, may also be implemented.
  • Reverse osmosis processes involving a filtration process that removes dissolved salts and metallic ions from water in which applied pressure on the concentrated side forces it through a semipermeable membrane may likewise be used.
  • examples of demineralization or ion removal technologies may include electrochemical operations, such as electrodialysis, electrodeionization, capacitive deionization and continuous electrodeionization (CEDI).
  • a demineralization unit may involve capacitive deionization, generally based on an electrostatic process operating at low voltages and pressures.
  • Produced water is pumped through an electrode assembly. Ions in the water are attracted to the oppositely charged electrodes. This concentrates the ions at the electrodes, while reducing the concentration of the ions in the water.
  • the cleaned water then passes through the unit. When the electrodes' capacity is reached, the water flow is stopped and the polarity of the electrodes is reversed. This causes the ions to move away from the electrodes, where they had previously accumulated.
  • the concentrated brine solution is then purged from the unit.
  • a continuous electrodeionization (CEDI) process may be implemented.
  • CEDI generally uses a combination of ion exchange resins and membranes and direct current to continuously deionize the water without the need for chemicals.
  • CEDI is an electrochemical process where an electrical charge is applied across the module.
  • Electrodes of electrochemical devices may generally be made of various materials, such as stainless steel, iridium oxide, ruthenium oxide and platinum. Electrodes may also be coated with various materials, for example, with titanium.
  • the electrodes cause the formation of H + and OH " ions.
  • the ions, along with the ions in the feed, are transported by the potential across the device.
  • the module is arranged with cells separated by membranes. The cell depth is about 0.1 inch.
  • the membranes allow only either anions or cations to pass. In this way, ionic species are concentrated in some cells, while other cells are depleted of ions.
  • the flow of ions is directly related to the electrical current applied to the module. Electrons do not flow across a cell. The electrons form ions and it is the ions that flow across the CEDI module.
  • the process typically relies on the use of cells separated by ionic membranes.
  • the conductivity of pure water is very low, so the required voltage to transport ions through pure water is very high.
  • Resins are used to increase conductivity in the water cells, which decreases the voltage requirement.
  • the resins are about 0.3 to about 0.5 mm spheres.
  • the surface of a resin has an ionic charge and is either cationic (c) or anionic (a).
  • Cationic resins have anionic functional groups, which attract cationic species (i.e. cationic resins are so called because they attract cations). In this way, cations can flow across the cell by traveling on the cationic resins.
  • anionic resins allow transport of anions. In application, many beds are mixed with both anionic and cationic resins, which allow transport of both types of ions across a cell.
  • the membranes are also made with cationic or anionic materials.
  • the IonPureTM (a Siemens company) membranes are fabricated by mixing the resins with polyethylene and extruding into sheets. This is called a heterogeneous structure.
  • the polyethylene provides the mechanical strength and the resin the transport properties. Cationic membranes only allow cations to pass while anionic membranes only allow anions to pass.
  • the resins and membranes When wetted, the resins and membranes may swell. Swelling causes the resins to exert a pressure on the walls and membranes of up to about 100 psi of force.
  • the resin material in the membrane also expands, which permanently alters the structure of a heterogeneous membrane.
  • the nominal leakage rate of an IonPureTM membrane is about 20 mI7hr/ft 2 /5 psi.
  • Sodium ions cause less swelling than hydronium ions. Therefore, in high strength brines the resin in the heterogeneous membrane will contract, causing the resin to become more porous.
  • Homogeneous membranes are made of only resin, and so allow a higher current flux. They are more expensive than heterogeneous membranes but are otherwise interchangeable.
  • Bipolar membranes are anionic membranes on one side and cationic on the other. They are the most expensive type of membranes and are used for water splitting. These membranes can be used in the place of a water splitting cell. They rely on water diffusion into the membrane and may not be appropriate for high rate production.
  • a power supply drives DC electrical current through the electrodes of the device.
  • the electrodes are the outermost cells on opposite sides of the module.
  • the electrode cells do not contain resin, but instead use a high strength brine to provide conductivity in the cell.
  • a plastic screen is placed in the cell to prevent the membrane from touching the electrode.
  • the cathode (-) is typically made from stainless steel, though other anode materials can also be used.
  • the electrons flow from the power source through this electrode. In the cathode cell, this causes the formation of hydroxide ions and hydrogen gas.
  • n H2 is the molar production rate of hydrogen gas (mole H 2 /second)
  • A is the electrical current (Amp)
  • F is Faraday's constant (96,485 coulomb/mole).
  • the anode (+) is titanium coated with a corrosion resistant conductor.
  • Conductors are typically platinum, iridium oxide, or ruthenium oxide. Iridium oxide is usually used as the coating in Siemens C-Series modules. For high amperage applications platinum may be a better material.
  • the electrons are pulled from water in the cell and are returned to the power source. This causes the formation of oxygen gas.
  • the production rate of oxygen is calculated from the below equation
  • ⁇ 02 is the molar production rate of hydrogen gas (mole O 2 /second)
  • A is the electrical current (Amp)
  • F is Faraday's constant (96,485 coulomb/mole).
  • operation of a treatment system 100 may involve a process stream being directed to an oxidation unit 1 10 from an industrial application 130.
  • An oxidation product stream exiting the oxidation unit 1 10 may be directed to a demineralization unit 120.
  • Demineralization unit 120 may produce a target compound stream, such as a sodium hydroxide stream. This stream may be directed back to the industrial application 130 for further use.
  • the target compound stream may be introduced directly to the industrial application 130 or may be mixed upstream thereof with fresh reactant from reactant source 140.
  • a discharge stream may be recycled back to the demineralization unit 120 for further processing and/or extraction of the target compound.
  • less fresh reactant may need to be added to industrial application 130 due to the production of reactant by the system from the process stream.
  • spent caustic may be treated to recover a sodium hydroxide product stream.
  • An ethylene plant or petroleum refinery plant may use fresh caustic, such as sodium hydroxide, to remove or scrub acid gases such as carbon dioxide and hydrogen sulfide from a process gas.
  • the fresh caustic may be about 50% NaOH in water, typically diluted to about 10% for use in the caustic tower. As much as about 8 tons of fresh caustic per hour may be consumed.
  • the caustic tower may also condense organic species such as mercaptans, light hydrocarbosn, acetaldehyde, and naphthenic and cresylic acids. As more acid is scrubbed, the amount of free caustic is reduced until it is no longer useful. At this point, the plants will typically remove the caustic from the system and it becomes known as spent caustic.
  • Typical spent caustic streams contain sodium carbonate, sulfides and high weight organic compounds dissolved in the solution.
  • the stream may typically have a high pH which retains the sulfide, carbonate, and organic acids in the liquid phase.
  • the stream may have a high content of dissolved solids, but is generally unsuitable for many demineralization processes because reactive sulfides and organic compounds may not be compatible with demineralaition processes, such as membrane materials of a CEDI system. Removal of the cations, such as sodium, would cause a release of the sulfide from the liquor, which in many cases is undesirable since hydrogen sulfide is a corrosive gas that is highly odorous and toxic.
  • the spent caustic liquor is oxidized using WAO and then demineralized using CEDI.
  • the oxidation converts the sulfides to harmless sulfate and the organic compounds to carbonate and short chain organic acids which are relatively stable and less disruptive to demineralization processes.
  • the oxidized liquor then passes to a CEDI process which removes a portion of the sodium to produce a sodium hydroxide product stream.
  • the residual stream is somewhat demineralized by the removal of the sodium ions, which also decreases the effluent pH.
  • One or more additional unit operations may be fluidly connected downstream of the demineralization unit.
  • a concentrator may be configured to receive and concentrate a target product stream, such as before delivering it upstream to an industrial operation for use.
  • Polishing units such as those involving chemical or biological treatment, may also be present to treat an effluent stream of the system prior to discharge.
  • the wet oxidation system may include a controller for adjusting or regulating at least one operating parameter of the system or a component of the system, such as, but not limited to, actuating valves and pumps.
  • Controller may be in electronic communication with at least one sensor configured to detect at least one operational parameter of the system.
  • the controller may be generally configured to generate a control signal to adjust one or more operational parameters in response to a signal generated by a sensor.
  • the controller is typically a microprocessor-based device, such as a programmable logic controller (PLC) or a distributed control system, that receives or sends input and output signals to and from components of the wet oxidation system.
  • Communication networks may permit any sensor or signal-generating device to be located at a significant distance from the controller or an associated computer system, while still providing data therebetween. Such communication mechanisms may be effected by utilizing any suitable technique including but not limited to those utilizing wireless protocols.
  • Tests 1-13 were performed in a Siemens C-Series CEDI module. The components are described below.
  • Cell type 1 which was a plastic frame filled with a 60/40 v/v mix of cationic and anionic resins.
  • the cross section profile of a cell (normal to the flow of current) consists of 3 cells in parallel.
  • the two outer chambers are 14"X 1.3125" and the central chamber is 14" x 1.25".
  • the total cross sectional area in a cell is 54.25" 2 (350 cm 2 ).
  • Cell type 2 also filled with a 60/40 v/v mix of cationic resin (The same frame is used, but inverted to direct flow to a different duct system).
  • Anode electrode - also made from iridium.
  • Each cell had one of three feed duct options and one of three discharge duct options:
  • Cell type 2 was ducted to feed DI water and to discharge NaOH product. In some cases the feed to cell type 2 was recycled NaOH product, instead of pure DI water.
  • the notation for representing the cell arrangement is: -S12S12S+.
  • the notation for representing the membrane arrangement is -caccac+.
  • the polarity was reversed, in which case the module becomes +S21 S21S-.
  • a schematic representing the operation of the module is shown in FIG. 3. Three different plumbing configurations were evaluated, shown in FIGS. 4A-4C, respectively.
  • Electrical power to the module was provided by a DC power supply and a power controller.
  • the power controller regulated the amperage to the module.
  • the controller displayed voltage and amperage.
  • Wiring was done by connecting the negative (black) wire into the cathode tab and the positive (red) wire into the anode tab.
  • the electrical system was capable of delivering no more than 8 or 9 amperes of power, above which the circuit breakers would trip.
  • the wires were 18 gauge and became warm to the touch after a few moments of operation.
  • Feed flow rates were monitored by the rotameters and effluent flow rates were monitored by use of a cylinder and stopwatch. pH, gas formation rate, and gas composition was not monitored. Formed gases were returned with the recycle brine to the feed tank and were vented by placing a vent hose near the feed tank.
  • FIG. 4D The plumbing configuration for these tests is shown in FIG. 4D.
  • the equipment was similar to that described in the prior tests, with the following exceptions:
  • the electrode plates had heavy titanium terminal tabs and platinum coated electrodes.
  • Tests 50 - 57 were conducted with the plumbing configuration shown in FIG. 4E.
  • the equipment was similar to that described in the prior tests, with the following exceptions:
  • the feed tank was first filled with the brine.
  • the DI water flow was turned on and the flow adjusted using the rotameter needle valve.
  • the main power was then turned on, which turned on the pumps. Flow rates and system backpressures were adjusted using the various control valves.
  • the DC power controller was energized and adjusted to the test amperage or voltage.
  • the conductivity and temperature of the feed and each effluent was measured and recorded using an ULTRAMETER 6P II conductivity meter commercially available from Myron L Co.
  • the system was allowed to stabilize for a number of minutes. Stabilization was monitored by using the conductivity meter.
  • the amperage and voltage was recorded, and samples of the feed, product NaOH and product brine were collected. For some studies, multiple samples were collected over a period of time.
  • the module was shut down by turning off the power and stopping the fresh DI water flow.
  • H 2 and O 2 gases are produced as bubbles in the brine.
  • the lower explosion limit (LEL) for H 2 is 4%. Fire and explosion hazards were mitigated by venting the brine return lines into a fume hood. For a hypothetical 4OA full-scale unit, 3 SCFM of air is estimated to be sufficient to dilute the H 2 to below 10% of the LEL. No LEL measurements were collected in this test work.
  • the feed and product samples were analyzed by HACH titration method #8203.
  • the titration was used to measure the NaOH, Na 2 CO 3 and NaHCO 3 content.
  • the Na 2 SO 4 concentration was measured by photometry using HACH method #8051.
  • the pH was monitored using the Myron L Co ULTRAMETER.
  • the NaOH, Na 2 CO 3 , and NaHCO 3 contents were monitored by titration using a Metohm 785 DMP Titrino autotitrator.
  • the feed composition was based on the likely content of an oxidized spent caustic. • 55 g/L Na 2 SO 4 • 3.1 g/L Na 2 CO 3
  • Tests 1 1 and 12 used a higher strength feed than listed above, which was prepared by doubling the salts dose and decanting the saturated supernatant from the mix tank.
  • Test 13 used a 1 A strength feed.
  • Tests 50-57 were performed using a solution of 80 g/L Na 2 CO 3 .
  • Test duration was the extent of time it took to record the parameters and collect samples, which was usually 1 to 5 minutes. The reported test time of day was recorded at the end of those steps.
  • the current efficiency is the fraction of the amperage that was utilized to transport sodium ions into the product NaOH stream.
  • the current efficiency is calculated from Faraday's law, using the following equation.
  • ⁇ Na is the molar flow rate of sodium in the product NaOH stream (mole
  • the module was disassembled.
  • One of the membranes was analyzed by SEM. This membrane separated the brine in the cathode cell from the DI water in the resin bed cell.
  • Tests 3, 4, and 5 were identical tests performed at identical conditions, with increased electrical current with each test.
  • the percent Na recovery and the concentration of Na in the product stream increased with increasing current.
  • the effluent temperature also increased.
  • the current efficiency decreased with increasing current. Decreasing current efficiency results in inefficient utilization of power and results in temperature increase.
  • Results are shown graphically in FIGS. 7A and 7B.
  • FIGS. 6A-6E shows the dynamic behavior of the current at high voltage.
  • FIG. 6C shows upon unit start-up the amperage initially increased with time. This was due to NaOH formation in the product cell, which increased conductivity and thus amperage at fixed voltage. At approximately 13:50 the current reached a maximum at 1 1 amps. After this, current steadily declined.
  • the system was subsequently designed with independently controlled flow and pressure to suspect cells in order to reduce or eliminate potential vapor locking, where formed H 2 , O 2 , and CO 2 gases might be collecting in stationary bubbles which grow with time.
  • sodium carbonate was substituted as the feed in order to reduce or eliminate CO 2 gas production from Na + removal. Loss of current with time was observed. The high current may have affected the surface of the membrane on the DI side.
  • Tests 1 1 and 12 were performed with similar feed and amperage. In these tests the NaOH product stream was recycled through cell type 2. Product NaOH exited the system through a small purge stream, which was replenished by DI water (i.e. feed and bleed). In this way, the flow rate of the stream across the cell was maintained high, but the overall residence time was increased to produce a smaller flowing stream of higher strength product.
  • DI water i.e. feed and bleed
  • Test 12 had a higher product discharge rate, and thus shorter caustic retention time. These tests were otherwise identical. The shorter retention time resulted in a weaker NaOH product stream, however the %Na recovery was 4 times higher than in test 11 and the current efficiency was also higher. These results imply longer caustic residence time can increase the strength of product, but may reduce overall Na recovery and electrical efficiency. This may be due to the high osmotic pressure of the caustic stream resisting transport of more Na + ions and may be overcome by using higher current.
  • Test 13 was conducted at similar conditions to 12, but with a lower strength feed brine. Test 13 was performed with carefully controlled differential pressure between cells, in an attempt to minimize cell/cell leakage. Test 13 was also conducted at a lower product discharge rate from cell type 2, in which a lower current efficiency and sodium recovery was expected prior to conducting this test. Surprisingly, this test showed better current efficiency and higher % Na recovery than test 12. It appears that using a weaker strength feed brine enhanced the sodium recovery.
  • Test 7 was performed at similar conditions to test 4.
  • Test 4 had a resin filled feed cell in the middle of the CEDI, while in test 7, this middle cell was filled with a screen.
  • Test 7 feed was a higher strength feed, which would also have had an impact on results, making review difficult, since two parameters are different.
  • the higher strength feed brine was expected to produce a lower current efficiency, however in the test 7 to test 4 comparison, the current efficiency is surprisingly approximately the same. This implies that replacing the resin with a screen does not diminish the efficiency of the process. All subsequent tests were performed with screens in the brine cells.
  • Tests 8 and 12 were similar tests. Test 8 was conducted with higher brine and caustic flow rates than test 12. The current efficiency of test 8 was higher than 12 and the product caustic strength was similar. These results may indicate that the higher flow rate of brine increases efficiency.
  • the process produced an off-gas in the brine recycle line.
  • the off-gas formation rate and composition was not measured.
  • the gas comprised primarily hydrogen and oxygen, formed on the electrodes.
  • CO 2 gas also evolved in tests that had NaHCO 3 in the feed, but no Na 2 CO 3 . Scanning electron microscope (SEM) results
  • the cationic membrane separating the cationic cell from the DI water cell was dried, gold sputtered, and placed in an SEM for analysis. Each side of the membrane was analyzed, and results are shown in FIGS. 7A and 7B.
  • the brine side image shows what appears to be resin particles suspended in the polyethylene sheet matrix. The cavities are larger than the particles, which is to be expected since the particles shrunk during the drying process, which was necessary in the sample preparation for the SEM.
  • the DI water side shows similar, however it appears that the sheet matrix is different and may indicate damage.
  • FIG. 2 The perceived plant flow diagram (PFD) for an ethylene plant is shown in FIG. 2.
  • Table 4 shows the mass balance for a plant where about 10% of the Na is recycled.
  • the product NaOH from the CEDI unit will be about 1.8 wt% NaOH at a flow of about 55% of the total spent caustic flow.
  • FIGS. 8A-8D Balances for several different configurations are shown in FIGS. 8A-8D.
  • FIG. 9 illustrates strength of NaOH in CEDI product stream to satisfy mass balance needs, such as may be based on similar balances.

Abstract

L'invention concerne des systèmes et procédés pour le traitement d'un flux de traitement. Le système de traitement peut généralement comprendre une unité d'oxydation couplée à une unité de déminéralisation aval. L'unité d'oxydation peut oxyder des contaminants organiques et de soufre réduit dans le flux de traitement pour faciliter le traitement aval. L'unité de déminéralisation peut convertir un produit de l'unité d'oxydation pour générer un flux minéral. Dans certains exemples, le flux de traitement peut être un flux de caustique épuisé provenant d'une opération industrielle, comme d'une installation de production d'éthylène ou d'une raffinerie. Un flux de caustique frais, comme un flux d'hydroxyde de sodium, peut être isolé dans l'étape de déminéralisation et renvoyé dans l'opération industrielle pour être utilisé.
PCT/US2007/026219 2006-12-22 2007-12-21 Systèmes et procédés pour le traitement d'un flux de traitement WO2008079362A1 (fr)

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CN101830587A (zh) * 2010-04-26 2010-09-15 烟台大学 一种处理重金属废水的工艺和装置
RU2448053C1 (ru) * 2010-10-20 2012-04-20 Виталий Владимирович Варцов Установка для очистки щелочных стоков
CN104909499A (zh) * 2015-06-10 2015-09-16 上海化学工业区中法水务发展有限公司 一种石化废水二级出水的处理方法
RU2749593C2 (ru) * 2017-11-16 2021-06-15 Андрей Владиславович Курочкин Установка для очистки сернисто-щелочных стоков

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ES2566536T3 (es) * 2010-07-01 2016-04-13 Emd Millipore Corporation Dispositivo y procedimiento de electrodesionización que comprende el control de la corriente eléctrica mediante la medición de la expansión del material de intercambio iónico
RU2485400C1 (ru) * 2011-10-13 2013-06-20 Общество с ограниченной ответственностью "Металлокрит" Способ обезвреживания отходов, содержащих углеводороды, с одновременным осаждением растворенных солей металлов и устройство для его осуществления
KR102458763B1 (ko) * 2016-08-23 2022-10-26 스완 아날라이티쉐 인스트루멘테 아크티엔게젤샤프트 액체의 전기 탈이온화 장치 및 방법

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CN101830587A (zh) * 2010-04-26 2010-09-15 烟台大学 一种处理重金属废水的工艺和装置
RU2448053C1 (ru) * 2010-10-20 2012-04-20 Виталий Владимирович Варцов Установка для очистки щелочных стоков
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RU2749593C2 (ru) * 2017-11-16 2021-06-15 Андрей Владиславович Курочкин Установка для очистки сернисто-щелочных стоков

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