EP4396139A1 - Systeme und verfahren zur online-steuerung einer chemischen behandlungslösung unter verwendung von kesselsteinsättigungsindizes - Google Patents

Systeme und verfahren zur online-steuerung einer chemischen behandlungslösung unter verwendung von kesselsteinsättigungsindizes

Info

Publication number
EP4396139A1
EP4396139A1 EP21956241.0A EP21956241A EP4396139A1 EP 4396139 A1 EP4396139 A1 EP 4396139A1 EP 21956241 A EP21956241 A EP 21956241A EP 4396139 A1 EP4396139 A1 EP 4396139A1
Authority
EP
European Patent Office
Prior art keywords
treatment solution
chemical treatment
process stream
applying
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21956241.0A
Other languages
English (en)
French (fr)
Inventor
Kevin Boudreaux
Bill GONZALEZ
Kerry KILLOUGH
Faycal Finnouche
David Oswald
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ChemTreat Inc
Original Assignee
ChemTreat Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ChemTreat Inc filed Critical ChemTreat Inc
Publication of EP4396139A1 publication Critical patent/EP4396139A1/de
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • 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
    • C02F2209/003—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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/005—Processes using a programmable logic controller [PLC]
    • C02F2209/006—Processes using a programmable logic controller [PLC] comprising a software program or a logic diagram
    • 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
    • C02F2209/005—Processes using a programmable logic controller [PLC]
    • C02F2209/008—Processes using a programmable logic controller [PLC] comprising telecommunication features, e.g. modems or antennas
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/05—Conductivity or salinity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/05—Conductivity or salinity
    • C02F2209/055—Hardness
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—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
    • C02F2209/07—Alkalinity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • Scaling occurs when the saturation index for a compound (e.g., calcium, silica, magnesium) is exceeded.
  • a scale saturation index represents the degree of saturation of water with respect to a specific compound. SSI calculations were developed to predict whether or not a water stream has a scaling or a corrosion tendency. Whether a water solution exceeds the SSI for a given compound, is affected by factors such as an increase or decrease in temperature, pH, and/or ionic concentrations.
  • PCW process cooling water
  • a non-transitory computer-readable medium stored in a memory and executed by a processor to execute PCW method steps for primary metal, iron, and steelmaking applications.
  • the steps may include sampling a plurality of characteristics of PCW using a plurality of sensors, calculating one or more of LSI/RSI based on the plurality of characteristics using a LSI/RSI measurement unit coupled to the plurality of sensors, and injecting one or more anti-scalant chemicals into the PCW responsive to the calculated one or more of the LSI and the RSI using an anti-scalant injection system to thereby control scale formation in the PCW.
  • Disclosed embodiments provide systems and methods that use LSI and RSI calculations to determine the scaling potential in the PCW and provide real-time adjustments in chemical dosing to the PCW circuit. This determination greatly reduces the scaling potential in a more comprehensive and economical manner from existing technologies.
  • the solution incorporates reliable monitoring of the salient parameters, which are used to calculate the LSI/RSI in real time via a PLC, and utilizes a feed-forward loop through the DCS to adjust chemical dosing based upon the data obtained.
  • the ability to calculate the scaling potential greatly improves the process performance and can extend the "run time" for the plant, which typically must shut down for water related scaling and fouling issues.
  • Embodiments include "building out” the needed instrumentation to measure pH, TDS, Temperature, Hardness, and Alkalinity (to calculate the LSI and RSI). This data is then integrated into a PLC algorithm that is fed into the DCS to compare current data versus setpoint LSI/RSI data. Deviations (+ or -) from the setpoint system data enable the anti-scalant pump to receive a 4/20ma signal to adjust the feed rate for the current situation.
  • Precipitation is governed by several water quality parameters: pH, hardness, alkalinity, temperature, and TDS. Precipitation will not occur under conditions that favor solubility, where salt concentration is lower than the saturation point. But environments that favor precipitation are common in cooling water circuits. In addition, as cooling water is lost to evaporation and drift, the components of scale are concentrated. This concentration, known as cycling, increases the scaling potential. Generally, the PCW system is treated with anti-scalants to minimize scale formation, but even with treatment, most plants have some scale formation. The origin of the scale is predominately from the calcium used for the iron ore coating with additional calcium coming from the level in the make-up water.
  • Precipitation occurs when the mineral saturation index of CaCO 3 is greater than one (1).
  • (Saturation Index > 1 is defined when the mineral salt concentration in the water phase can no longer remain dissolved in water).
  • LSI addresses the concept of mineral saturation using pH as a main variable.
  • LSI can be interpreted as the pH change required to bring water to equilibrium. Water with a LSI of 1.0 is one pH unit above saturation. Reducing the pH by 1 unit will bring the water into equilibrium. This occurs because the portion of total alkalinity present as CO 3 ' 2 decreases as the pH decreases, according to the equilibria describing the dissociation of carbonic acid:
  • LSI Scale can form and CaCO 3 precipitation may occur; and If LSI is close to zero: Borderline scale potential, water quality or changes in temperature, or evaporation, could change the index.
  • RSI attempts to correlate scale thickness observed to the water chemistry. Like the LSI, the RSI has its basis in the concept of saturation level. RSI is given by:
  • RSI 2(pH s ) - pH where: pH is the measured water pH; and pH s is the pH at saturation in calcite or calcium carbonate.
  • pH is the measured water pH; and pH s is the pH at saturation in calcite or calcium carbonate.
  • indices are very important models used for the process water systems of a DRI-PCW system, as well as Blast Furnace and Steelmaking water systems, because they all have a general tendency to become scale forming under the operating conditions.
  • the LSI and RSI models are used extensively, as mentioned, throughout the industry, but scale control technology within the DRI, Iron, and Steelmaking industries have only indirectly used these models to aid in scale control of the process. There is no real-time monitoring or controlling of these water systems to add the required level of treatment. The best technology available can only run off-line laboratory LSI/RSI tests, but rarely are adjustments made even if the tests are run.
  • FIG. 2 illustrates real time pH observed over time using the pH sensor according to embodiments.
  • FIG. 3 is a schematic diagram of one embodiment of the LSI/RSI-based anti-scalant dosing feedback control loop of the disclosed PCW system.
  • a pH sensor 24, a TDS sensor 26, a temperature sensor 28, a calcium hardness sensor 30, and a total alkalinity titer (TAC) sensor 32 are in communication with the cold well 22 of the PCW system 10.
  • the pH sensor 24 includes a solid state analyzer for monitoring the pH of the industrial water.
  • the TDS sensor 26 indirectly monitors by conductance, utilizing conductivity probes with 2 or 4 electrodes that enable the building of a conductivity analyzer loop providing easy measurement and signal relay to the PLC.
  • the factor for TDS is 0.7 * Conductance in pS/cm.
  • the temperature sensor 28 in includes a thermometer.
  • the various sensors are all coupled to a LSI/RSI measurement unit 34 and/or the DCS 36 of the PCW system 10, the latter of which controls all higher functions of the PCW system 10.
  • the LSI/RSI measurement unit 34 calculates the LSI/RSI using the sensor data. This provides an LSI/RSI feedback loop 50 for anti-scalant injection.
  • the memory 110 may include any of volatile memory elements (e.g., random access memory (RAM, such as DRAM, SRAM, SDRAM, etc.)), nonvolatile memory elements (e.g., ROM, hard drive, tape, CDROM, etc.), and combinations thereof. Moreover, the memory 110 may incorporate electronic, magnetic, optical, and/or other types of storage media. Note that the memory 110 may have a distributed architecture, where various components are situated remotely from one another but can be accessed by the processor 102.
  • the software in memory 110 may include one or more software programs, each of which includes an ordered listing of executable instructions for implementing logical functions.
  • the software in the memory 110 includes a suitable operating system (O/S) 114 and one or more programs 116.
  • O/S operating system
  • the DCS 38 directs the injection of anti-scalant into the cold well 22 of the PCW system 10 (or otherwise) based on the LSI/RSI calculation.
  • the scale inhibitor injection system 38 includes an appropriate dosing pump and conduit, as is well known to those of ordinary skill in the art.
  • Scale inhibitors are specialty chemicals that are added to water to delay, reduce and/or prevent scale deposition. Compounds based on acrylic acid polymers, maleic acid polymers and phosphonates have been used extensively for scale treatment in water systems due to their excellent solubility, thermal stability and dosage efficiency. In the water treatment industry, the major classes of scale inhibitors are inorganic phosphate, organo phosphorous, and organic polymer backbones. The below lists many candidates that may be used per the disclosed embodiments:
  • PAAS polyacrylic acid sodium salt
  • HPMA Hydrophilic Anhydride
  • AA AMPS Copolymer copolymer of acrylic acid and 2-acrylamide-2- methyl propane sulfonic acid
  • the online pH sensor may have a measurement capability at real-time, /. ⁇ ., continuously, or at near real-time, or intervals with a testing frequency being within predetermined intervals.
  • the intervals may be less than 5 minutes, less than 10 minutes, less than 15 minutes, less than 20 minutes, less than 30 minutes, less than 1 hour, less than 2 hours, less than 6 hours, or less than 12 hours.
  • the intervals may be in the range of 1 minute to 24 hours, 1 minute to 12 hours, 5 minutes to 12 hours, 10 minutes to 6 hours, 15 minutes to 2 hours, 20 minutes to an hour, or 30 minutes to an hour.
  • the frequency employed in measurements taken in the disclosed embodiments may depend on the particular system. For example, it will be understood that the scale inhibition dynamics of the specific system.
  • the pH sensor of the disclosed embodiments is made of materials that are customized to the environment that they are to be used in, and are designed to chemically withstand the environment and exhibit wear resistance caused by aggressive gasses and abrasion from high-velocity solids.
  • the electronic transmission function uses latest technology. Solid state construction can be completely sealed and customized to the environment. Internal O-rings can be omitted as these degrade and are prone to failure. Gels and electrolytes are preferably not used as these can easily contaminate and increase maintenance. A large surface area is used that reduces fouling and improves reliability. Glass characteristics result in very low drift and reliable readings over prolonged periods — 2-4 weeks. Glass construction cam be highly durable, and double and triple-junction construction provides long life.
  • the programmatic tools used in developing the disclosed machine learning algorithms are not particularly limited and may include, but are not limited to, open source tools, rule engines such as Hadoop®, programming languages including SAS®, SQL, R and Python and various relational database architectures.
  • Examples of well-known computing systems, environments, and/or configurations that may be suitable for use with the disclosed embodiments may include, but are not limited to, personal computer systems, server computer systems, thin clients, thick clients, handheld or laptop devices, multiprocessor systems, microprocessor-based systems, set top boxes, programmable consumer electronics, network PCs, minicomputer systems, mainframe computer systems, and distributed cloud computing environments that include any of the above systems or devices, and the like.
  • the computer system may be described in the general context of computer system executable instructions, such as program modules, being executed by a computer system.
  • program modules may include routines, programs, objects, components, logic, data structures, and so on that perform particular tasks or implement particular abstract data types.
  • the computer system may be practiced in distributed cloud computing environments where tasks are performed by remote processing devices that are linked through a communications network.
  • program modules may be located in both local and remote computer system storage media including memory storage devices.
  • the water system may be, for example, a once-through system 210, as illustrated in FIG. 6, or a recirculating system 220, as illustrated in FIG. 7. These systems including cooling components, such as heat exchangers, for cooling water flow streaming through the systems.
  • the once-through system 210 includes a flow path defined by water sourced from a natural water source that is pumped through a heat exchanger 211 via pump 215 and returned to the same or different water source 212.
  • the recirculating system 220 includes a flow path defined by water sourced from a natural water source 222 that is pumped through a heat exchanger 221 via pump 225 and then enters the atmospheric cooling tower 226 after leaving the heat exchanger 221 to be cooled by the cooling tower then recirculated through the system.
  • feed system D is controlled based on the results computed by the PLC, as shown in FIGS. 6 and 7.
  • the systems 210 and 220 may also include a data storage 214,224 for storing various dosage and amount schemes implemented by the controller 213,223, as seen in FIGS. 6 and 7.
  • the disclosed online SSI calculation and chemical feed embodiments can be used in conjunction with mineral process systems. These systems typically involve treating a heap of crushed and agglomerated ore with an appropriate lixiviant (e.g., a diluted alkaline cyanide solution) to dissolve the metals (leachate), collecting the leachate in a pond or tank (pregnant or value bearing solution), processing the pregnant solution to recover the metals, and recycling the barren solution (with additional lixiviant) back to the heap.
  • an appropriate lixiviant e.g., a diluted alkaline cyanide solution

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
EP21956241.0A 2021-09-02 2021-09-02 Systeme und verfahren zur online-steuerung einer chemischen behandlungslösung unter verwendung von kesselsteinsättigungsindizes Pending EP4396139A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2021/048843 WO2023033825A1 (en) 2021-09-02 2021-09-02 Systems and methods for online control of a chemical treatment solution using scale saturation indices

Publications (1)

Publication Number Publication Date
EP4396139A1 true EP4396139A1 (de) 2024-07-10

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ID=85411536

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21956241.0A Pending EP4396139A1 (de) 2021-09-02 2021-09-02 Systeme und verfahren zur online-steuerung einer chemischen behandlungslösung unter verwendung von kesselsteinsättigungsindizes

Country Status (2)

Country Link
EP (1) EP4396139A1 (de)
WO (1) WO2023033825A1 (de)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6641754B2 (en) * 2001-03-15 2003-11-04 Betzdearborn Inc. Method for controlling scale formation and deposition in aqueous systems
US20030127391A1 (en) * 2001-07-26 2003-07-10 Craft Frank S. Method for treatment of circulating cooling water
US8377279B2 (en) * 2003-11-13 2013-02-19 Siemens Industry, Inc. Water treatment system and method
US8980101B2 (en) * 2008-09-04 2015-03-17 Nalco Company Method for inhibiting scale formation and deposition in membrane systems via the use of an AA-AMPS copolymer
US8153010B2 (en) * 2009-01-12 2012-04-10 American Air Liquide, Inc. Method to inhibit scale formation in cooling circuits using carbon dioxide
WO2011068859A1 (en) * 2009-12-02 2011-06-09 Schlumberger Canada Limited Heap leach operations
US11542187B2 (en) * 2019-01-25 2023-01-03 Nouryon Chemicals International B.V. Composition and method for controlling scale in industrial water systems
US11780742B2 (en) * 2020-04-24 2023-10-10 Chemtreat, Inc. Methods for online control of a chemical treatment solution using scale saturation indices

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Publication number Publication date
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