WO2013122593A1 - Procédé d'adoucissement d'eau à efficacité élevée - Google Patents

Procédé d'adoucissement d'eau à efficacité élevée Download PDF

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Publication number
WO2013122593A1
WO2013122593A1 PCT/US2012/025498 US2012025498W WO2013122593A1 WO 2013122593 A1 WO2013122593 A1 WO 2013122593A1 US 2012025498 W US2012025498 W US 2012025498W WO 2013122593 A1 WO2013122593 A1 WO 2013122593A1
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water stream
water
contaminants
solids
adjusting
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PCT/US2012/025498
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English (en)
Inventor
Ken V. PANDYA
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Pandya Ken V
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Priority claimed from US13/398,648 external-priority patent/US9056784B2/en
Publication of WO2013122593A1 publication Critical patent/WO2013122593A1/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
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/206—Manganese or manganese compounds
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • 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
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
    • 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
    • C02F2209/001—Upstream control, i.e. monitoring for predictive control
    • 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
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • 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
    • C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
    • 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
    • C02F2209/20—Total organic carbon [TOC]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness
    • C02F5/06—Softening water by precipitation of the hardness using calcium compounds

Definitions

  • This invention relates generally to water treatment / purification processes and, specifically, to water-softening processes which are effective in treating highly contaminated surface waters, well waters, waste waters, produced waters, and process effluent waste streams.
  • the novel water-softening process disclosed herein is effective for a broad range and level of contaminants. Specifically, it is particularly well-suited for removing a broad (but, unfortunately, common) array of contaminates (namely calcium, magnesium, barium, strontium, copper, zinc, iron, manganese, aluminum, silica, TOC [total organic carbon], oil, grease, TDS [total dissolved solids] and TSS [total suspended solids]).
  • contaminates namely calcium, magnesium, barium, strontium, copper, zinc, iron, manganese, aluminum, silica, TOC [total organic carbon], oil, grease, TDS [total dissolved solids] and TSS [total suspended solids]
  • the novel softening process can utilize carbon dioxide and/or carbon monoxide in alkaline solution, thus creating bicarbonate or carbonate ions by chemical reaction.
  • the novel water-softening process disclosed herein can work with soda ash, potassium hydroxide, or sodium hydroxide as the chemical agents.
  • novel water-softening process disclosed herein can be carried out at ambient temperatures, although the rate of reaction will be faster at elevated temperatures.
  • the novel water-softening process disclosed herein utilizes very little energy; in fact, in most cases, the energy consumption comes from mixing devices and transfer pumps. Furthermore, the novel water-softening process can be carried out under atmospheric pressure or at elevated pressures.
  • the novel water- softening process disclosed herein does not require expensive materials of construction such as high-quality alloys.
  • inexpensive materials such as polyvinyl chloride (hereinafter "PVC"), fiberglass, carbon steel, or stainless steel, can be used.
  • PVC polyvinyl chloride
  • fiberglass fiberglass
  • carbon steel or stainless steel
  • the novel water-softening process disclosed herein can be carried out in presence of excess amounts of coagulation aid chemicals.
  • the novel water-softening process is intended for a broad range of contaminations. It uses a high-pH mode of operation by using chemicals such as soda ash and/or sodium hydroxide, potassium carbonate, or potassium hydroxide and is intended to treat surface waters, seawater, produced waters from oil and gas drilling operations, and wastewaters from municipal as well as industrial applications.
  • novel water-softening process disclosed herein is not an ion exchange process.
  • Ion exchange processes are mostly batch processes; they generally achieve water softening by exchanging ions on an ion exchange resin. Once the ion exchange resin is fully exhausted (i.e., it has no further capability for exchanging hardness for, e.g., the sodium ion or the hydrogen ion), it has to be regenerated, typically, by either a sodium chloride solution (NaCl), a hydrochloric acid solution (HC1), or a sulfuric acid solution (H 2 SO 4 ).
  • NaCl sodium chloride solution
  • HC1 hydrochloric acid solution
  • SO 4 sulfuric acid solution
  • novel water-softening process disclosed herein is extremely efficient in terms of producing high-quality effluent while simultaneously generating a minimum volume disposal stream.
  • a typical sludge / waste stream from the novel water-softening process can be reprocessed to recover the water stream, thus making the novel water-softening process an important part of any zero liquid discharge (hereinafter "ZLD") process.
  • ZLD zero liquid discharge
  • Zero liquid discharge (hereinafter "ZLD") technologies utilize a combination of pretreatment processes such as those described in the sections hereinabove.
  • the resultant process stream is typically further treated with acid or scale inhibitors to lower scale-forming tendencies and/or to prevent further precipitation or scaling due to silica, calcium, magnesium, barium and/or strontium salts.
  • acid or scale inhibitors to lower scale-forming tendencies and/or to prevent further precipitation or scaling due to silica, calcium, magnesium, barium and/or strontium salts.
  • the effluent pH from the pretreatment is lowered (to less than about 5) to reduce the scaling potential due to the presence of calcium, magnesium, strontium and/or barium.
  • the lower pH effluent is typically highly aggressive on conventional metals such as carbon steel or lower grades of stainless steel, and requires the use of exotic (and expensive) metallurgy such as titanium alloys, Hastalloy C, and/or Alloy 20.
  • novel water-softening process effluent with pH values typically exceeding 10.5, do not require lowering of pH; thus, the metallurgy of the equipment downstream of the novel water-softening process can be fabricated from lower-cost alloys such as carbon steel, grade three zero four stainless steel (hereinafter "304 SS”), three hundred sixteen stainless steel (hereinafter "316 SS”), or Duplex stainless steel or Super duplex stainless steel or SMO 254.
  • 304 SS grade three zero four stainless steel
  • 316 SS three hundred sixteen stainless steel
  • SMO 254 Duplex stainless steel or Super duplex stainless steel or SMO 254.
  • non-metallic materials such as polyvinyl chloride (hereinafter “PVC”), chlorinated PVC (hereinafter “CPVC”), polypropylene (hereinafter “PPL”), Teflon (hereinafter “PTFE”), or fiberglass reinforced plastic (hereinafter “FRP”).
  • PVC polyvinyl chloride
  • CPVC chlorinated PVC
  • PPL polypropylene
  • PTFE Teflon
  • FRP fiberglass reinforced plastic
  • the treated effluent from the novel water-softening process can be further treated by concentration processes or ZLD processes such as reverse osmosis, electro-dialysis, evaporators, or crystallizers. Concentrated streams from these processes can be highly pure, sterile, and could be recycled or reused for further industrial or non-industrial uses (such as, for example, dry salt or chemicals manufacturing processes). Concentrated streams from these processes can also be recycled or reused to "kill" gas wells after completion of gas extraction process. [00030] In view of the continuing need for an improved process to efficiently and effectively remove contaminates from water streams, an improved high-efficiency water- softening process for removing contaminates has been developed.
  • one embodiment of the invention is a process for removing at least some contaminants selected from the group consisting of Ca, Mg, Ba, Sr, Cu, Zn, iron, Mn, Al, Si0 2 , TOC, oil, grease and TDS and TSS from a contaminated water stream, the process including steps of: (a) collecting a quantity of the water stream containing the contaminants for treatment; (b) analyzing the quantity of the water stream containing the contaminants for a composition and an amount of the contaminants in the quantity of the water stream; (c) adding at least one of carbonate or bicarbonate to the quantity of the water stream in an amount at least equivalent to the contaminants in the quantity of the water stream; (d) adjusting the pH of the quantity of the water stream to a value from about 10.5 to 14; (e) separating the solids from the quantity of the water stream; and (f) recovering water containing a reduced contaminant content.
  • the process including steps of: (a) collecting a quantity of the water stream containing the contaminants for treatment; (b) analyzing the
  • a process for removing at least some contaminants selected from the group consisting of Ca, Mg, Ba, Sr, Cu, Zn, iron, Mn, Al, Si0 2 , TOC, oil, grease, and TDS and TSS from a contaminated water stream includes steps of: (a) analyzing the water stream containing the contaminants for a composition and an amount of the contaminants in the water stream; (b) adding at least one of carbonate or bicarbonate to the water stream in an amount at least equivalent to the contaminants in the water stream; (c) adjusting the pH of the water stream to a value from about 10.5 to 14; (d) separating the solids from the water stream; and (e) recovering the water stream containing a reduced contaminant content.
  • FIGURES 1A and IB exemplify a piping / instrumentation drawing showing several aspects of one embodiment of the novel water-softening process disclosed herein;
  • FIGURE 2 exemplifies a piping / instrumentation drawing showing several aspects of an alternate embodiment of the novel water-softening process disclosed herein, the alternate embodiment comprising a reactor clarifier for performing the processes T-201, T-202, T-203, T-204 of the embodiment of Figs. 1A and IB;
  • FIGURE 3 exemplifies a piping / instrumentation drawing showing several aspects of a rotary drum vacuum filter of the novel water-softening process disclosed herein, the rotary drum vacuum filter being adaptable for replacing or supplementing the process T-204 of Figs. 1 A and IB;
  • FIGURE 4 exemplifies a piping / instrumentation drawing showing several aspects of a carbon dioxide unit embodying features of the novel water-softening process disclosed herein;
  • FIGURE 5 exemplifies steps in a process utilizing coagulation aid chemicals in accordance with one preferred embodiment of the present invention
  • FIGURE 6 exemplifies steps of a process utilizing a mechanical separator device in accordance with an alternate preferred embodiment of the present invention.
  • FIGURE 7 exemplifies a polyelectrolyte chemical structure.
  • the novel, high-efficiency water-softening process disclosed herein is a process that is extremely effective in treating highly contaminated surface waters such as well waters, waste water and process effluent streams.
  • the process disclosed facilitates the effective removal and/or reduction of certain inorganic contaminants such as calcium (Ca), magnesium (Mg), barium (Ba), strontium (Sr), iron (Ferrous Fe++ or Ferric Fe+++), manganese (Mn), zinc (Zn), and silica (Si0 2 ), as well as certain species such as oil, grease, total organic carbon (hereinafter “TOC”), biochemical oxygen demand (hereinafter “BOD”), total suspended solids (hereinafter “TSS”), and colloidal material.
  • TOC total organic carbon
  • BOD biochemical oxygen demand
  • TSS total suspended solids
  • waste streams that contain moderate to high levels of these species can also be a problem.
  • industries and municipal agencies are required to eliminate the disposal of such streams.
  • the waste streams can be disposed of by means of deep-well injection; however, those streams must be pretreated in order to remove certain objectionable species such as iron, manganese, suspended solids, and TOC.
  • the initial calcium and magnesium hardness level exceeded 10,500 mg/1, expressed as CaC0 3 .
  • Presence of such high levels of impurities can be found in highly concentrated waste streams, such as produced waters from oil and gas drilling operations, concentrated cooling tower blow-downs, reject streams from waste water recovered oil applications, landfill leacheate, and superfund sites.
  • novel water-softening process is effective, in part, because it introduces carbonate (C0 3 ) and hydroxyl (OH) species to form precipitates under high-pH conditions, typically in a pH range of 10.5-14.0.
  • Certain species such as silica, oil and grease can be co-precipitated or adsorbed on the carbonate, bicarbonate, hydroxyl or sulfate precipitates.
  • coagulating aid chemicals such as alum, ferric chloride, ferric sulfate, cationic or anion polymers, and polyelectrolyte chemicals
  • the precipitated material could remain in solution which could be filtered out by cross-flow membrane processes such as Microfiltration or Ultrafiltration.
  • Carbonate and bicarbonate species can be derived from naturally occurring chemical compounds such as quick lime (CaO), hydrated lime (Ca(OH) 2 ) or soda ash (Na 2 C0 3 ).
  • novel water-softening process also allows for the addition of selected cations, such as Ca or Ba, to precipitate excess amounts of anions such as S0 4 and C0 3 at pH levels of 10.5 - 14.0.
  • selected cations such as Ca or Ba
  • the precipitated materials may be removed from the treated water stream by utilizing treatment processes such as settling, clarification, filtration, and/or advanced membrane separation.
  • treatment processes such as settling, clarification, filtration, and/or advanced membrane separation.
  • step 502 in this first step a quantity of same or all of the contaminated process streams may be collected in a storage tank, pond or other vessel. If the feed water composition is known to vary, better results are obtained if mixing, either via mechanical mixers, aeration blowers, or close recirculation of the liquid waste streams, is effected so as to create as homogeneous a solution as possible.
  • step 504 it is helpful to analyze the composition of the quantity of the process stream, including Ca, Mg, Na, Ba, Sr, K, HC0 3 , S0 4 , CI, Si0 2 , N0 3 , Fe, Mn, oil and grease, TOC, pH, total dissolved solids (hereinafter "TDS”), conductivity, and TSS.
  • the composition of the quantity of the process stream including Ca, Mg, Na, Ba, Sr, K, HC0 3 , S0 4 , CI, Si0 2 , N0 3 , Fe, Mn, oil and grease, TOC, pH, total dissolved solids (hereinafter "TDS”), conductivity, and TSS.
  • tank T-201, mixer M-201, chemical feed systems CF-201A and CF-201B for adding barium chloride, lime, hydrated lime, and/or soda ash and with reference to the alternative embodiment of FIG. 2, C0 3 addition tank T-201 at reactor clarifier T-201, and with reference to FIG. 5, step 506, a calculated amount of carbonate or bicarbonate alkalinity is added in an amount at least stoichiometrically equivalent to the incoming amount of Ca, Mg, Sr, Ba and other impurities.
  • Carbonate ions may also be created by reaction of pure carbon dioxide or waste carbon dioxide or waste carbon monoxide.
  • exhaust from a diesel generator or a natural gas burning machine may be combined with a strongly basic solution such as sodium hydroxide or potassium hydroxide.
  • carbonate ions are then formed at a pH higher than 8.2.
  • waste carbon dioxide or waste carbon monoxide is advantageous for several reasons. Putting any waste component to work is environmentally friendly and prudent; however, in light of recent concerns raised by some scientists that excess waste carbon dioxide and waste carbon monoxide potentially contributes to the greenhouse effect and/or global warming, the additional benefits of this approach towards implementation / execution of the invention become obvious.
  • tank T-202, mixer M-202, chemical feed system CF-202 for adding NaOH, or KOH or other strong base and with reference to the alternative embodiment of FIG. 2, chemical feed system CF-202 for adding OH at reactor clarifier T-201, and with reference to FIG. 5, step 508, a basic solution, such as sodium hydroxide or potassium hydroxide, is added to raise the operating pH to between about 10.5 and about 14.0. Homogeneous solutions are preferably created by mixing.
  • the desired pH range is preferably 12-14 and it is in this range that complete contaminant removal of the type desired occurs; however, it has also been observed that suboptimal, but nonetheless very good, results are observed in the pH range of 10.5-12.0.
  • tank T-203, mixer M-203, chemical feed system CF-203 for adding alum, ferric chloride, ferric sulfate, and/or polymer and with reference to the alternative embodiment of FIG. 2, chemical feed system CF-203 for adding a coagulation aid chemical at reactor clarifier T-201, and with reference to FIG. 5, step 510, the required amount of coagulation aid chemical (such as ferric chloride, alum, polymer, or the like) is added to create a floe.
  • a homogeneous solution is preferably created by mixing.
  • alum aluminum ammonium sulfate, aluminum potassium sulfate, aluminum sodium sulfate, aluminum sulfate
  • ferric chloride ferric sulfate
  • polymers and polyelectrolyte chemicals represent, as a class, the most commercially important coagulation aid chemicals in use today.
  • a low-cost waste stream comprising spent caustic soda solution (25% NaOH) and aluminum, which was used in an aluminum extrusion process to etch out aluminum metal from extrusion dyes, has been used effectively as a coagulation aid agent.
  • the process stream itself may contain flocculation aid chemicals.
  • the waste alkali solution may contain flocculation aid chemicals.
  • external dosing of coagulation aid chemicals may not be required or, at a minimum, could be minimized.
  • An example of such a stream is a waste caustic stream, such as that referenced above, from an aluminum fabrication plant; often, such caustic streams contain a substantial level of aluminum. Coagulants are typically used at pH values below about 10.5.
  • step 512 a measured amount of polyelectrolyte is preferably added to aid the filtration and solids-settling process.
  • a homogeneous solution is preferably created by adding mixing energy.
  • polyelectrolyte is a generic term known in the water treatment industry (analogous to the term “PVC” to the non-metallic fabricator).
  • Polyelectrolyte chemicals are generally high-molecular-weight, long-chain organic chemicals with either positive or negative charge (the type being selected based on the nature of the electrical charge found on precipitate).
  • coagulation aid polymers and the polyelectrolyte chemicals are used in the water softening process.
  • the coagulation aid and the polyelectrolyte may be added together or separately to a quantity of the process stream. For example, one might employ alum and a cationic polymer to make solids heavier and settle down. Then, one might end up with a small level of excess polymer that will tend to float away or bypass the system. However, by adding a polyelectrolyte of opposite charge, one can capture the small floating materials, still representing suspended solids, and make a secondary precipitation to achieve greater clarification. Polyelectrolytes are typically used at pH values below about 10.5.
  • PSS poly(sodium styrene sulfonate)
  • PAA poly(acrylic acid)
  • Polyelectrolytes are polymers whose repeating units bear an electrolyte group. These groups will dissociate in aqueous solutions (water), making the polymers charged. Polyelectrolyte properties are thus similar to both electrolytes (salts) and polymers (high molecular weight compounds), and are sometimes called polysalts. Like salts, their solutions are electrically conductive. Like polymers, their solutions are often viscous. Many biological molecules are polyelectrolytes. For instance, polypeptides (thus all proteins) and DNA are polyelectrolytes. Both natural and synthetic polyelectrolytes are used in a variety of industries.
  • FIG. 1A depicts removal of most of settled solids, and in tank T-204 where sludge is removed, though some small level of lighter solids can escape, the treatment of which is discussed in further detail below.
  • FIG. IB depicts mechanical separation by media filter and cartridge filter.
  • FIG. 2 depicts the removal of settled solids by filter press and, in FIG. 3, the removal of suspended solids by rotary drum vacuum filter.
  • FIG. 1A, T-103, exemplifies removal of oil and lighter floe.
  • the solids are allowed to settle in a process that is commonly known as settling or clarification. Heavier solids, mostly carbonate or bicarbonate precipitates and metal hydroxide precipitates, settle and some of the lighter suspended solids, such as oil and grease, light organic matter, silica and colloidal material, get adsorbed onto the carbonate and hydroxide precipitates, and settle with other solids.
  • Heavier solids mostly carbonate or bicarbonate precipitates and metal hydroxide precipitates, settle and some of the lighter suspended solids, such as oil and grease, light organic matter, silica and colloidal material, get adsorbed onto the carbonate and hydroxide precipitates, and settle with other solids.
  • Reaction time for completing the various process steps may vary depending on the nature of water stream. In most cases, utilizing typical commercial mechanisms, a thirty- minute reaction time is sufficient although, in select applications, the reaction may continue for several hours or days.
  • the alkalinity, pH adjusters, the coagulant and electrolytes (reagent), may be added together or at the same time or over very short periods as well as separately at time periods selected based upon properties of the specific contaminants in the treated stream or batch of contaminated water. In either event, the treatment with each reagent is carried out at a pH from 10.5 to 14.
  • the contaminated water stream may be treated in selected quantities in a batch process or with the same or similar reagents in an in-line process wherein the reagents are added separately or together into a flowing stream of the contaminated stream. In either case, the treatment with all of the reagents either together or separately is at 10.5 to 14.
  • the process of the present invention is effective to remove contaminants from highly contaminated water streams.
  • the reduction of most of the contaminants is greater than ninety percent as shown in Table 1. While the contaminants have been greatly reduced, the treated water is generally not suitable as potable water, but could be an acceptable stream for disposal or recycle without further treatment or as a feed stream which could be further purified for disposal to the environment.
  • the removal of a high level of contaminants as achieved by the present process is highly desirable for treating many industrial processes which produce highly contaminated by-product streams.
  • step 516 settled solids are preferably separated from the supernatant process solution. Solids can be removed from the bottom of a reactor vessel by means of a reaction clarifier or sludge thickener. In some cases, a scraper mechanism may be added to facilitate the removal of suspended solids. The clarified stream is collected in a storage vessel or other container for further processing.
  • a portion of the sludge can be re-circulated to further aid settling of the precipitated and suspended solids.
  • filter press FP 301 and with reference to the alternative embodiment of FIG. 2, filter press FP-301 , and with reference to FIG. 5, step 518, solids may separate from a thickened sludge and may be recovered from the reactor vessel by using a mechanical device such as a filter press, vacuum press, rotary drum vacuum filter, membrane filter, ultrafilter, or microfilter. Clear liquid is recovered and recycled for further use, and solids are preferably recovered as a filter cake. The filter cake can be dried to recover the precipitated solids. The solids can be recycled for further use.
  • a mechanical device such as a filter press, vacuum press, rotary drum vacuum filter, membrane filter, ultrafilter, or microfilter.
  • Clear liquid is recovered and recycled for further use, and solids are preferably recovered as a filter cake.
  • the filter cake can be dried to recover the precipitated solids.
  • the solids can be recycled for further use.
  • FIGURE 6 exemplifies an alternative embodiment of the invention, similar to FIG. 5, but in which it may be preferable to not add the coagulation aid chemical of step 510, and keep the precipitated solids in suspension.
  • steps 510-516 of FIG. 5 are preferably replaced by a step 616, depicted in FIG. 6, wherein precipitated solids, along with other suspended solids and colloidal solids, are preferably removed from the bulk stream by using a mechanical, solid-liquid separator, such as an advanced filtration process, such as a rotary drum vacuum filter, filter press, media filter, membrane filter, ultra-filter system, micro-filter system, or the like.
  • a mechanical, solid-liquid separator such as an advanced filtration process, such as a rotary drum vacuum filter, filter press, media filter, membrane filter, ultra-filter system, micro-filter system, or the like.
  • the number of process / reaction steps, as described above, may be reduced by combining several steps.
  • the desired chemical reaction associated with a particular step or steps will be sufficiently fast so that in-line addition of chemicals (rather than addition of chemicals directly to a reactor) is possible.
  • the chemical reaction will be sufficiently fast, and reaction time sufficiently short, that minimizing the size of the reactor unit or adding the reagents to a flowing contaminated stream may be possible.
  • the seeded slurry process can provide effective results.
  • a known amount of salts (example: CaS0 4 ) are added to the reactor vessel to promote fast chemical reaction.
  • novel water-softening process disclosed herein can be usefully employed for the recovery of precious minerals such as calcium, magnesium, barium, strontium, iron, and manganese.
  • waste chemicals such as waste alkali from industrial operations, demineralizer regeneration operations, waste alkali from aluminum or iron fabrication processes, waste potash (potassium carbonate), or waste potassium hydroxide could be used in place of pure chemicals.
  • waste chemicals such as waste alkali from industrial operations, demineralizer regeneration operations, waste alkali from aluminum or iron fabrication processes, waste potash (potassium carbonate), or waste potassium hydroxide could be used in place of pure chemicals.
  • waste gases such as carbon dioxide or carbon monoxide could be combined with an alkaline solution such as sodium hydroxide or potassium hydroxide to form bicarbonate or carbonate ions.
  • alkaline solution such as sodium hydroxide or potassium hydroxide
  • bicarbonate or carbonate ions can then react with the incoming Ca, Mg, Ba, or Sr to form the precipitate.
  • sulfate ions can be added to form a precipitate.
  • Sulfate ions can be derived from the use of certain inorganic salts such as barium sulfate.
  • crushed lime, hydrated lime or pulverized soda ash can be considered.
  • One way to create a sodium carbonate or sodium bicarbonate or potassium carbonate or potassium bicarbonate solution is to react carbon dioxide with sodium hydroxide or potassium hydroxide in a reactor column. Specifically, a sodium hydroxide or potassium hydroxide solution is sprayed in an absorption column that comprises a reactor vessel, internal distributors and a mass-transfer packing (structured packing or dumped packing).
  • Carbon dioxide (C0 2 ) and/or carbon monoxide (CO) gas is preferably introduced at the bottom of the reactor vessel in a counter-current manner. Excess air or ozone can be added to enhance reaction of carbon monoxide. After reaction, either the sodium carbonate or potassium carbonate solution is collected in the receiver vessel, ready for use. At a pH above 8.2, one expects to find mostly carbonate species. At a pH below 8.2, one expects to find an equilibrium of bicarbonate and carbon dioxide.

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

L'invention concerne un procédé d'adoucissement d'eau à efficacité élevée. Le procédé d'adoucissement d'eau est particulièrement efficace pour traiter les eaux de traitement contenant une large gamme de contaminants, tels que Ca, Mg, Ba, Sr, le fer, l'aluminium, le manganèse, le cuivre, le zinc, le silice, TOC, de l'huile, et de la graisse. Le procédé d'adoucissement d'eau comprend les étapes consistant à : (a) l'ajout d'ions carbonate et d'ions hydroxyde auxdites eaux de traitement jusqu'à ce que le pH de traitement s'élève à, entre, au niveau de ou environ 10,5 et au niveau de ou environ 14,0; (b) l'ajout éventuel d'une aide à la coagulation de manière à faciliter la création de solides séparés comprenant une partie substantielle des contaminants; (c) l'ajout éventuel d'un polyélectrolyte de manière à faciliter la création de solides séparés comprenant une partie substantielle des contaminants; et (d) la séparation par phase des solides séparés de manière à éliminer les contaminants et à produire des eaux de traitement hautement purifiées.
PCT/US2012/025498 2012-02-16 2012-02-16 Procédé d'adoucissement d'eau à efficacité élevée WO2013122593A1 (fr)

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US13/398,648 US9056784B2 (en) 2006-09-19 2012-02-16 High efficiency water-softening process
US13/398,648 2012-02-16

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CN108640316A (zh) * 2018-05-31 2018-10-12 苏州品立环保系统有限公司 餐饮废水处理设备
CN110156249A (zh) * 2018-03-27 2019-08-23 新疆水处理工程技术研究中心有限公司 一种基于管式膜的高浓度印染废水预处理的集成方法

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US1653272A (en) 1921-12-09 1927-12-20 Gen Zeolite Company Process of purifying water
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CN110156249A (zh) * 2018-03-27 2019-08-23 新疆水处理工程技术研究中心有限公司 一种基于管式膜的高浓度印染废水预处理的集成方法
CN110156249B (zh) * 2018-03-27 2022-02-18 新疆水处理工程技术研究中心有限公司 一种基于管式膜的高浓度印染废水预处理的集成方法
CN108640316A (zh) * 2018-05-31 2018-10-12 苏州品立环保系统有限公司 餐饮废水处理设备
CN108640316B (zh) * 2018-05-31 2021-04-06 苏州品立环保系统有限公司 餐饮废水处理设备

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