CN104185764A - Method and device for preventing corrosion in hot water systems - Google Patents

Method and device for preventing corrosion in hot water systems Download PDF

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Publication number
CN104185764A
CN104185764A CN201380015117.0A CN201380015117A CN104185764A CN 104185764 A CN104185764 A CN 104185764A CN 201380015117 A CN201380015117 A CN 201380015117A CN 104185764 A CN104185764 A CN 104185764A
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China
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orp
district
real
time
hot
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CN201380015117.0A
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Inventor
P·D·海克斯
D·A·格兰特安
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ChampionX LLC
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Ondeo Nalco Co
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Priority claimed from US13/442,324 external-priority patent/US8771593B2/en
Application filed by Ondeo Nalco Co filed Critical Ondeo Nalco Co
Publication of CN104185764A publication Critical patent/CN104185764A/en
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24HEATING; RANGES; VENTILATING
    • F24DDOMESTIC- OR SPACE-HEATING SYSTEMS, e.g. CENTRAL HEATING SYSTEMS; DOMESTIC HOT-WATER SUPPLY SYSTEMS; ELEMENTS OR COMPONENTS THEREFOR
    • F24D19/00Details
    • F24D19/0092Devices for preventing or removing corrosion, slime or scale
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/008Control or steering systems not provided for elsewhere in subclass C02F
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F15/00Other methods of preventing corrosion or incrustation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/20Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • C02F1/302Treatment of water, waste water, or sewage by irradiation with microwaves
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • C02F1/32Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/70Treatment of water, waste water, or sewage by reduction
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02Non-contaminated water, e.g. for industrial water supply
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/001Upstream control, i.e. monitoring for predictive control
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/005Processes using a programmable logic controller [PLC]
    • C02F2209/006Processes using a programmable logic controller [PLC] comprising a software program or a logic diagram
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/005Processes using a programmable logic controller [PLC]
    • C02F2209/008Processes using a programmable logic controller [PLC] comprising telecommunication features, e.g. modems or antennas
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/04Oxidation reduction potential [ORP]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/08Corrosion inhibition

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)

Abstract

Disclosed is a method of controlling a real-time oxidation-reduction potential in a hot water system to inhibit corrosion in the hot water system. The method includes defining one or more operational protective zones in the hot water system. One or more of the operational protective zones includes an oxidation-reduction potential probe that is operable to measure a real-time oxidation-reduction potential in the hot water system at operating temperature and pressure. The probe transmits the measured real-time potential to the controller, which assesses and interprets the transmitted potential to determine whether it conforms to an oxidation-reduction potential setting. If the measured potential does not conform the oxidation-reduction potential setting, the controller is operable to feed or remove one or more active chemical species into or from the hot water system and further operable to change at least one system parameter.

Description

Be used for the method and apparatus of the corrosion that prevents hot-water heating system
The cross reference of related application
The application is that the sequence number of submitting on July 24th, 2007 is 11/782, the part of 192 U.S. Patent application present co-pending " Method and Device for Preventing Corrosion in Hot Water Systems " continues, and its disclosure is integrated with herein by reference with its entirety.
Technical field
The present invention relates generally to the method that reduces or suppress the corrosion in hot-water heating system.More specifically, the present invention relates to measure the real-time oxidation-reduction potential under operating temperature and the pressure in one or more operation protections district and use the adjusting of the parameter of those measurement result control effect oxidation-reduction potentials.The invention particularly relates to part and/or the overall situation reduces or suppresses the corrosion in simple or complicated hot-water heating system.
Background technology
Hot-water heating system substantially comprises full Ferrous Metallurgy or mixes metallurgy, such as copper or copper alloy system, nickel and nickel-base alloys and stainless steel, and can mix with mild steel composition.There is the hot-water heating system of many general classes/assemblies, such as boiler, hot-water heater, heat exchanger, steam generator, nuclear energy power system, internal combustion engine and diesel engine cooling system, evaporator system, hot desalting system, papermaking operation, sweat etc. and attached auxiliary equipment.They are the dynamic operation systems that stand countless REDOX Stress events (, any electrochemical events in the hot-water heating system relevant with change in oxidation or reduction potential).Such event comprises oxidation-reduction potential (" the ORP ") space that involves in system or any processing of system substantially.
These events are caused by numerous factors, comprising: from the leakage of each assembly, pollution, fault pump, sealing, vacuum line and measuring instrument from leakage air.In addition the use of the increase of heavy-oxygen-enriched water, (such as boiler water-filling, the steam condensate (SC) returning and/or original ground surface water or underground water, oxygen-eliminating device fault, steam and turbine load swing and about the problem of chemicals feed pump) causes unplanned reduction or increase in chemical treatment feed rate.Uncontrolled REDOX Stress event may cause serious etching problem, such as localized corrosion, stress burn into corrosion fatigue and/or hot-water heating system in mobile accelerated corrosion problem.With regard to their essence, these problems are electrochemical and therefore attach environment and the interactional redox property of structural material often.
Identify the REDOX Stress event in hot-water heating system although put into practice now some conventional methods, due to hot-water heating system dynamics, thereby most REDOX Stress event is uncertain.Do not put into practice widely these methods, because they have intrinsic shortcoming (seeing below).As a result, most REDOX Stress event is not detected and is not corrected.Uncontrolled REDOX Stress event may cause the serious etching problem in these systems, and this has affected shop equipment life expectancy, reliability, production capacity, security, environmental planning, Capital expenditure and total shop equipment running cost negatively.
Identification REDOX Stress event comprise at present in-line meter and grab sample wet chemical analysis method of testing the two.In these two methods, first sample must stand sample adjustment before measuring, such as cooling.The example of in-line meter comprises dissolved oxygen meter, cation electrodeposition conductance instrument, room temperature ORP instrument, pH instrument, sodium analyzer, hardness analysis instrument, than conductivity meter, silicon meter, particle and nephelometer, reducing agent analyzer etc.Typically, make sample cooling after or carry out at elevated temperatures the general corrosion monitoring such as sample and electrochemical analysis.Grabbing sample method of testing comprises analysis dissolved oxygen, pH, hardness, silica electrical conductivity, amounts to soluble iron, copper and silica, reducing agent excess etc.
Some shortcomings of these methods comprise as follows.Grab sample analyze preset time measure in a single point and be not therefore the variable continuous monitoring method for REDOX Stress event.It also usually has not enough low-level detection boundary.Whether in-service monitoring device does not provide the direct measurement result of REDOX Stress and therefore can not indicate REDOX Stress event to occur in any specific time.Corrosion monitoring device detects general corrosion, but can not measure the change in the local corrosion speed being caused by REDOX Stress event.Online reducing agent analyzer is measured the quantity of reducing agent, instead of system under system temperature and pressure by the clean REDOX Stress standing.Therefore REDOX Stress may occur in the obvious existence of reducing agent is another shortcoming of this technology.
Dissolved oxygen (" DO ") meter has similar shortcoming.Measure DO (oxidant) quantity (but clean REDOX Stress that not necessarily system is standing) be not corrosion stress accurate index.Sample also must be cooled before DO measures, and had therefore increased and had detected the lag time of REDOX Stress event aspect when starting.In addition, may cause inaccurate reading for the current potential of the oxygen consumption of sample line.In the time of obviously not the existing of DO, also may there is REDOX Stress, and pettiness in sample or there is no DO may be that mistake negates potentially.In addition, all instrument as described above are relatively costly for purchase, and require calibrate frequently and safeguard.
Corrosion sample has provided the time averaging result of General System corrosion.In addition, this technology does not provide real-time instruction or the control of REDOX Stress event.Online electrochemical corrosion instrument is not enough to determine and can not use at low conductivity environment for localized corrosion.
Room temperature ORP is the direct measurement result of the clean ORP of the sample obtained from system.The shortcoming of this technology is, it is failed instruction, under system temperature and pressure, what is occurring.Usually can not at room temperature observe the REDOX Stress event occurring under operating temperature and pressure, this is because process kinetics and thermodynamics change along with temperature.In addition, room temperature ORP measurement device is more blunt and more may become polarization.The reliability of such equipment is not good enough, and they need to be calibrated frequently and safeguard.
Therefore, there are the lasting needs of developing monitor and being controlled at the method for the real-time ORP in the hot-water heating system under operating temperature and pressure.
Summary of the invention
Therefore, the disclosure provide a kind of under operating temperature and pressure Real-Time Monitoring and control the method for the ORP in hot-water heating system.The numerous processes that occur in hot-water heating system contribute to ORP, this ORP and then serve as the REDOX Stress index for hot-water heating system.Main and the less important REDOX Stress event contrary with conventional indoor temperature measurement, the ORP measurement result obtaining in real time under system operating temperature and pressure occurs in can real time indication system.Real-time ORP monitoring like this can be used to measure, REDOX Stress demand in identification and evaluating system and can serving as directly or corrosion process index indirectly.
In one aspect, the invention provides and a kind ofly control real-time ORP in hot-water heating system to reduce or to suppress the method for the corrosion in hot-water heating system.Described method comprises the one or more operation protections district (" zone " or " zones ") limiting in hot-water heating system.Select limit in district at least one (for example, one, two or more), and one or more (for example,, two or more) in selected district comprise at least one ORP probe that can operate to measure real-time ORP and communicate by letter with controller.When hot-water heating system is during in operating temperature and pressure, for example, selecting one or more (, one, two or more) in district to locate or measure continuously or off and on described real-time ORP.Described method also comprises that it is that measured real-time ORP or the ORP that calculates based on measured real-time ORP meet ORP and arrange that measured real-time ORP is sent to controller and assessment.Described ORP arranges and can be or arrange or arrange for the different ORP of at least two in selected district for each the identical ORP in selected district.If measured real-time ORP or the ORP that calculates do not meet ORP and arrange, so described method comprises the parameter changing in hot-water heating system.In an embodiment, if measured real-time ORP or the ORP that calculates do not meet ORP and arrange, so described method comprises at least one in execution action below: (i) one or more active chemistries of effective dose are fed in hot-water heating system, (ii) remove one or more active chemistries of effective dose from hot-water heating system, and (iii) change systematic parameter.
In another aspect, the invention provides a kind of corrosion control equipment for hot-water heating system.Described hot-water heating system has one or more (for example, one, two or more) operation protection district, wherein selects the subset in district (preferably two or more district).In an embodiment, described equipment comprises the receiver of communicating by letter of popping one's head in one or more ORP.Activate the subset of ORP probe, and each activated ORP probe can operate to measure real-time ORP in operating temperature and pressure place.At least one ORP probe is arranged on the one or more places in selected district.In an embodiment, described equipment also comprises processor, and described processor can operate to resolve the measured real-time ORP that is delivered to receiver from each activated ORP probe.Described processor or directly resolve measured real-time ORP or the ORP that calculates based on measured real-time ORP.In an embodiment, corrosion control equipment can operate to change based on measured and one or more in ORP of being resolved or regulate parameter.
According at least one embodiment, feed apparatus is communicated by letter with conveyer, and described feed apparatus can operate to manage introduces in hot-water heating system one or more active chemistries to affect the change in real-time ORP.In at least one embodiment, can operate to remove one, chemical removing device and the corrosion control devices communicating of two or more chemical substance from hot-water heating system.If the real-time ORP that resolves does not meet ORP and arranges, so described processor can operate to send output signal by conveyer to feed apparatus or chemical removing device.
An advantage of the invention is and provide a kind of operating temperature based in hot-water heating system and pressure place measure real-time ORP and in hot-water heating system, maintain ORP and arrange so that measured ORP is made a response by one or more active chemistries are fed into, thereby suppress the method for the corrosion in hot-water heating system.
Another advantage of the present invention is to provide a kind of hot-water heating system corrosion control equipment, comprises that collaborative work is to control receiver, processor, conveyer and the feed apparatus of the real-time ORP in the one or more operation protections district in hot-water heating system.
Another advantage of the present invention be by enable system parameter through improved maintenance and control and increase hot-water heating system efficiency.
Another advantage of the present invention is by preventing that exactly corrosion from reducing the running cost for various hot-water heating systems and assembly.
Aforementionedly feature of the present invention and technological merit are summarized quite largo to can understand better detailed description of the present invention below.Below will the of the present invention additional feature and advantage of the theme that forms claim of the present invention be described.Those skilled in the art should understand, and disclosed design and specific embodiment can easily be used the basis that makes an amendment or be designed for other embodiment that carries out identical object of the present invention.Those skilled in the art it will also be appreciated that such embodiment of equal value does not depart from the spirit and scope of the present invention that the claim as enclosed is set forth.
Brief description of the drawings
Fig. 1 has described the hot-water heating system of 3 assemblies of simplifying, and wherein makeup water stream is through " oxygen-eliminating device ", " FW pump " with enter " boiler ", and this boiler and then generation " useful steam " are for the use subsequently in each processing.
Fig. 2 illustrates the boiler configuration that comprises that multiple feed pumps, multiple heat exchanger and steam generator are more complicated.
Fig. 3 has described respectively " ORP control zone ", and wherein arrange can be for the system at various temperature and difference for ORP.
Fig. 4 illustrates at the multiple REDOX active materials of various positions feeding to control the T of single position (trade mark of Nalco Company).
Detailed description of the invention
As used herein, " hot-water heating system ", " system " refer to similar term any system that wherein hot water contacts with metal surface." hot water " means to have the water from the temperature of about 37 DEG C to about 370 DEG C.System can be at atmospheric pressure or under up to the pressure of about 4000psi or operate lower than it.
" ORP ", " T ORP ", " at-T ORP " and " ORP in real time " refer to the oxidation-reduction potential for the industrial water system under operating temperature and pressure.In some example in this article, ORP is indicated as room temperature ORP.
" ORP probe " refers to any equipment that can measure and transmit real-time ORP signal.Although can use any applicable equipment, but the sequence number present co-pending of submitting to is 11/668, in 048 U.S. Patent application " High Temperature and Pressure Oxidation-Reduction Potential Measuring and Monitoring Device for Hot Water Systems ", disclose preferred equipment, described application is integrated with herein by reference with its full text.Typically, ORP probe comprises Temperature Detector, noble metal electrode and reference electrode.
" active chemistry " refers to oxidant, reducing agent, corrosion inhibitor, corrosive agent and impact or changes other material of the ORP in hot-water heating system.Such material has below been described in more detail.
" REDOX Stress " refers to or any electrochemical events in the hot-water heating system relevant with change in oxidation or reduction potential directly or indirectly.
" controller system ", " controller " and similarly term refer to manual operator or have the electronic equipment of assembly, described assembly such as processor, memory devices, digital storage media, cathode-ray tube, liquid crystal display, plasma display, touch-screen or other monitor and/or other assembly.In some instances, controller can be used to the following integrated: one or more special ICs, program, computer executable instructions or algorithm, one or more hard wired devices, wireless device and/or one or more plant equipment.Some or all in controller system function can be at the center position such as the webserver for the communication on LAN, wide area network, wireless network, internet connection, microwave link, infrared link etc.In addition can comprise such as other assembly of signal-conditioning unit or System Monitor to promote signal processing algorithm.
In one embodiment, method comprises automation controller.In another embodiment, controller is manually or half manual, the wherein chemical composition of operator's analytic signal and definite feedwater (" FW "), such as oxygen or other oxide, oxygen scavenger or other reducing agent, corrosion inhibitor and/or corrosion dosage.In an embodiment, by resolving measured ORP signal according to the controller system of described method control FW chemical composition.In an embodiment, controller system is also resolved measured temperature and is determined and add or the amount of the active chemical agent (if any) that removes.Except add or remove from the one or more chemical substances in hot-water heating system or substitute add or remove from the one or more chemical substances in hot-water heating system, controller system can also operate to determine whether need change or regulating system parameter material.Temperature Detector also may be used to such as the information object in warning scheme and/or control program.Should understand, control program other input and other water constituent/character based on such as pH, DO level can comprise pump limiter, warning, Based Intelligent Control and/or analog.
Should anticipate, disclosed method is applicable to comprise that direct and satellite active chemical agent feeding designs the various hot-water heating systems of the two." directly " feeding typically refers to the real-time ORP at measurement zone place and active chemical agent is fed into identical district." satellite " feeding typically refers to the real-time ORP at measurement zone place and active chemical agent is fed into different districts.Representational system and system component comprise condenser, pipe side and shell-side the two; Heat exchanger; Pump; Sealing; Mild steel or copper base FW heater; Cu-based alloy surface condenser; Oxygen-eliminating device; Water pipe and multitubular boiler; Paper machine; Condensed water receiver; There is or do not have the steam condensate (SC) transfer conduit of Automatic steam trap Trap; Process liquids heat exchanger; Evaporimeter; Desalting system; Fresh water condenser; The water source of desuperheat; Mobile accelerated corrosion protection; Air heater; For the engine cooling system of diesel oil and gasoline; Etc..
Other exemplary processing comprises papermaking processing, such as Kraft slurrying and bleaching; Wafer polishing and planarization (for example, silicon wafer polishing); Burning gases discharge (for example, SO 2, NO x, mercury); Fermentation process; Ground heat treatment; And water-soluble organic oxidation reduction synthetic (requiring the polymerization processing of redox initiator).
Conventional corrosion control system is used the feeding of a point.Disclosed the present invention uses target feeding by appropriate amount/dosage of accurately determining needed active chemical agent and those chemicals.For example, can distinguish such as the relative zoneofoxidation of low pressure FW heater (copper base metallurgy) with more reducing zones with high pressure FW heater (non-copper base metallurgy) to alleviate the relevant problem of accelerated corrosion that flows.Relative oxidizing condition in all iron FW heaters at the part place of pressurized water reactor is relative with the final FW heater of the relative reduction system of stress corrosion cracking alleviating for steam generator.
The present invention can detect and the two is made a response to main and less important REDOX Stress event.Typically, implementor knows system corrosion control implication and possible REDOX stressor and can therefore select one or more suitably to monitor the T ORP space to fixed system in limited operation protection district.Like this, thus by the local and/or long-range T ORP reading feeding based on as main REDOX Stress index or remove REDOX active material to control corrosion be possible.Monitoring and measurement T ORP space are assessed and recognition system demand, and then described system requirements compare to react, solve and control REDOX Stress event with the tolerance of known/formulation.As the index of less important REDOX Stress, the present invention can detect the corrosion process being caused by previous main REDOX Stress, and wherein main REDOX stressor is no longer obvious.
ORP probe can detect the several different factor of the REDOX Stress event contributing in hot-water heating system.For example, the probe of the ORP in selected district can serve as the direct indicator of the corrosion in this district or another district.In an embodiment, if the measured real-time ORP at the first selection place of district or the ORP calculating do not meet for the ORP in the first selection district arrange, in the first selection district, measure so real-time ORP and one or more active chemistries are fed into the first selection district.In another embodiment, arrange if measured real-time ORP or the ORP that calculates do not meet for the ORP in the first selection district, measure so real-time ORP at the first place of selection district and at the one or more active chemistries of one or more other selected district place's feeding.In another embodiment, one or more real-time ORP are measured at one or more places in selected district, and one or more in one or more real-time ORP based on measured select districts to calculate one or more other real-time ORP for one or more other.
As mentioned above, in some cases, the measured ORP in the firstth district is used to calculate the ORP for another district.Such calculating can complete about the various hypothesis of system dynamics or by temperature/hydrochemical compositions difference of measuring between each district by carrying out.The approximate condition that uses thermodynamic principles well-known to those having ordinary skill in the art and mixed potential theory also to think about other things in district.But such calculating typically stands intrinsic inaccuracy; Therefore, preferred method is in selected district, to measure on the spot real-time ORP.
Exist several important factors for determining or be defined for the concrete operation protection/control zone of system.The target of any particular system is the T ORP " the boiler dedicated best practices of shop equipment " realizing for this system.For example, some shop equipment is because control theory, environmental constraints, economics, industrial standard etc. are limited to some chemical composition.System temperature can also be from a shop equipment to another shop equipment and dynamic change, and this requirement is adjusted in the concrete control theory adopting being explained in more detail in example below.Different shop equipments can also have unique REDOX Stress baseline, and may need to determine the unwise change to baseline.
Other factors comprises the concrete OPR change material of having a mind to interpolation or intrinsic existence; Be used for the engineering alloy of the structure of the each several part/entity of system; Desired general and local corrosion is alleviated; Dose limiting; Other system material details; Special consideration, such as mobile accelerated corrosion, stress and corrosion cracking; System change.It should be appreciated by those skilled in the art that how assessing these and other system variable/material details realizes the present invention for concrete shop equipment or system.
Ideally, any part of shop equipment can be used T ORP to make its T ORP REDOX Stress measured and control.That is to say, REDOX active material is fed directly into a concrete equipment (or group of equipment), and the T ORP that measures on the spot and control the water in this part equipment is for corrosion alleviation.The present invention more specifically solves the adverse effect of following of this corrosion transmission in other place in the local corrosion of shielded one or more parts and the transmission of corrosion product and system, comprises dirt, heat-transfer area coating, turbine deposition etc.Such full monitoring of equipment and control method are due to system constraint and economics and be usually impossible.Therefore, the each several part of system typically needs to process as whole entity.In some cases, the whole feedwater chain of steam generator system may be described entity.Alternatively, only the group of the fraction of system or the each several part of system is described entity.Should anticipate, can select and monitor/control any part, assembly or entity (comprising the whole system that is regarded as an entity).
In one aspect, arrange and can limit or selected area overlapping with another for the ORP in a selected district.In another aspect, for the ORP in a selected district arrange limit with other or selected district completely independent.In aspect another, for the ORP in a selected district arrange depend in part on one or more other limit or selected district in factor.
In an embodiment, determine that for the first selection district ORP arranges, and determine that for additional selection district (if any) additional ORP arranges alternatively.In one embodiment, determine that independently each additional ORP arranges.Alternatively, one or more in arranging of ORP can depend on that one or more other ORP arrange.ORP arranges and substantially depends on and performance constraint based on hot-water heating system.
Can reach the ORP setting that is identified for any particular system by any applicable method.Sequence number is 7,666, in 312 United States Patent (USP) " Method of Inhibiting Corrosion in Industrial Hot Water Systems by Monitoring and Controlling Oxidant/Reductant Feed through a Nonlinear Control Algorithm ", described preferred method, described patent is integrated with herein by reference with its entirety.But, should anticipate, any method well-known to those having ordinary skill in the art can be used to find out that ORP arranges.In an embodiment, ORP setting is the ORP set point of selecting from one or more single values.In another embodiment, ORP setting is the ORP setting range of selecting from one or more scopes of value.Along with the past of time, can regulate or change the ORP setting for any selected district.For example, given shop equipment can have the timetable that different time arranges for the ORP of the different piece/assembly of system that is summarized in.This timetable is typically by the operation factors in the system based on changing along with the demand change about system.
Some districts may keep relative reduction, and relatively more polyoxy of other district.For example, with reference to figure 2, heat exchanger 1 and 2 may be manufactured by the alloy of showing low corrosion rate under more reducing conditions.But heat exchanger 3 may be manufactured by the different metallurgy of showing lower corrosion rate under more oxidizing conditions.Then, may also need under more reducing conditions, keep " steam generator ".By corresponding adjusting and monitoring T ORP control zone to compensate these difference.
In one embodiment, one or more in selected district can be in monitoring and/or alarm mode, and one or more other selected district is in control model.In an embodiment, the selected district in monitoring and/or alarm mode can switch between these patterns.Such switching can or manually be controlled or be automatic.Below present T ORP tMsystem can be used to several examples that REDOX Stress controls.
In another embodiment, stride across any pump and measure T ORP with testing pump or seal erosion or inefficacy.In another embodiment, method can be used to detect heat exchanger pipeline and leak, for example, because a kind of active chemical agent material may be transferred to the other end (, shell-side is to pipe side, and vice versa) by the leakage in heat exchanger.Another example will be that surface condenser cooling water leakage is in FW condensed water hot well.In another embodiment, method can be used to detect any undesired intrusion of exterior active chemicals material (, systemic contamination thing).In interchangeable embodiment, T ORP can be used to form " fingerprint " of the concrete REDOX stressor in system.Like this, when more boiler water-fillings along with REDOX stress follow and increase and while adding system to every now and then, it can be with the warning system in advance that acts on boiler pipe and break.
ORP value measured or that calculate can be indicated the amount of the electroactive substance in one or more in selected district.Can or directly see or infer such instruction in another district of directly not measuring ORP in measurement ORP district.In some cases, measured or the chemicals amount of amount of the electroactive substance in the ORP that the calculates instruction one or more selected districts of remote-effects.In more typical situation, electroactive substance directly affects ORP measured or that calculate.
In one embodiment, method comprises that from selected district after trigger event is to another the oblique ascension in selected district.Causing drift in the real-time ORP in one or more control zones or any event of change can be trigger event.Those of ordinary skill in the art can analyze such option and select the one or more trigger events for system.For example, making the other parts online (or making its off-line) of pump or system can be trigger event.Owing to using and changing such as the downstream between turbine drive and the use of other lower pressure, thereby steam pressure change, this also can be selected as trigger event.Triggering can also be based on activating the various condensation flow that can introduce concrete REDOX stressor in system.Such trigger event can detect by probe, relay, monitor etc., keeps can detecting by the change in the real-time ORP in one or more control zones simultaneously.In addition, the speed of the change of these and other event can the ramp-up rate of instruction from a control zone to another control zone, comprises instantaneous, timing, step-by-step movement or other applicable oblique ascension pattern.
Representational trigger event can also comprise that the operation of a lot of timings or timetable or other shop equipment are dynamic.Timetable may be fixing start-up time, is the oblique ascension in time in some system operations subsequently.For example, initiate FW flow after 30 minutes, in real time ORP should be in the 100mV of desired ORP setting.After fully loaded 20 minutes of firing of boiler, ORP should arrange to ORP on slope in real time.In the time that other place in the system such as upstream component reaches ORP and arranges, also can trigger described slope.For example, once upstream control region has reached its ORP, (or for example in 50mV) is set, control zone, downstream is activated or enters in control model.The sequence that real-time ORP like this controls is the method for optimizing triggering.
Changing shop equipment dynamically also can initiate to trigger and/or slope.In an embodiment, trigger event can comprise that shop equipment power stage changes.For example, the minimizing of 5% power stage can be the trigger event that the real-time ORP in the one or more control zones in initiation system changes.May be for example to change the signal immediately of ORP setting or the gradual change slope to new ORP setting for one or more control zones for initiating the processing of real-time ORP change.Speed or amplitude that this processing can decline based on power.In addition, triggering and/or slope mechanism may be the interrelated of multiple signals and regularly complicated.
In a preferred embodiment, the change to FW chemical composition and adjusting comprise other active chemical agent that adds or remove (in the time of possibility) oxygen or other oxidant, oxygen scavenger or other reducing agent, corrosion inhibitor, corrosive agent and/or FW.According to definition, oxygen scavenger is reducing agent, but not every reducing agent must be oxygen scavenger.The reducing agent that is suitable as oxygen scavenger meets the thermodynamics requirement that exothermic reaction and oxygen coexist.For actual application, typically require reasonably reactive at low temperature place.That is to say, should have some good kineticses.In addition, such as other change to FW chemical composition for system control and corrosion control with regulate and can comprise and add/remove other oxidant (oxidizing agent or oxidant), other reducing agent (reducing agent or reductant) and/or other activity or inertia chemicals.
Reducing agent and its oxidation product are not corrosive and do not form corrosive product in the time that they form in steam generation equipment.Typically, some oxygen scavenger plays a role best and is affected by the catalytic action in a mode or another way in some pH scope, temperature and pressure.Can the knowledge based on criterion discussed in this article and those skilled in the art easily be identified for the selection to the suitable oxygen scavenger of fixed system.
Preferred reducing agent (, oxygen scavenger) comprise hydrazine, sulphite, bisulfites, N, N-N, N-diethylhydroxylamine, hydroquinones, erythorbate or arabo-ascorbic acid, methyl ethyl ketoxime, azanol, hydroxymalonic acid, ethoxyquin, the methyl tetrazone (methyltetrazone), durol diamines thing, semicarbazides, diethylaminoethanol, MEA, the acid of 2-ketone grape, ascorbic acid, boron hydride, isopropylhydroxyla, gallic acid, dihydroxyacetone (DHA), tannic acid and its derivative, food grade antioxidants, analog, and any combination.Should understand, in method of the present invention, can use any active chemistry.
Representational oxidant comprises base form, analog and the combination of oxygen, hydrogen peroxide, organic (alkyl and aryl) peroxide and peracid, ozone, quinone, acid and nitrate and nitrite.
Representational corrosive agent comprises inorganic acid (for example, HCl, H 2sO 4, HNO 3, H 3pO 4) and their salt/derivative; Caustic alkali (for example, Na, K, Li, hydroxide); Ammonium hydroxide; Chelant, such as EDTA, NTA, HEDP; Phosphonic acids and polyphosphonic acid; Phosphonate ester; Water-soluble and/or dispersible organic polymer complexing agent, such as acrylate homopolymer, copolymer and terpolymer; Acrylamide; Acrylonitrile; Methacrylic acid; Styrene sulfonic acid; Analog; And combination.
Representational corrosion inhibitor comprises alkali and phosphatic amine salt and polyphosphate; Neutralizing amine; Molybdate; Tungstates; Borate; Benzoic acid salt; Film forming corrosion inhibitor, such as alkyl, thiazolinyl and aryl polyamines and their derivative; It is disclosed surface activator composition in 5,849,220 United States Patent (USP) such as sequence number; It is disclosed oligomeric organic phosphoric acid chemicals in 5,023,000 United States Patent (USP) such as sequence number.
In another embodiment of the present invention, remove one or more chemical substances from hot-water heating system.For example, can process and remove oxygen from the by-pass flow of main processing water via film.Any applicable film can be used to such remove and those skilled in the art will select applicable film and by-pass flow processing.Nitrogen or lower oxygen concentration carrier gas (or the by-pass flow of main processing water) may reside in a side of gas permeation film, and process the opposite side of water at film.The oxygen existing in the by-pass flow of main processing water leaves the by-pass flow of main processing water to stride across balanced its partial pressure of film by diffusion, and then, this will reduce the oxygen content in main processing water and reduce ORP.In an embodiment, can comprise oxygen-eliminating device (referring to for example, the configuration of Fig. 1) or similarly degassing processing for example, leave main system to utilize adverse current steam (thering is lower dissolved oxygen value) mechanically to remove or remove non-condensing gas (, oxygen).Therefore main system stream make its ORP be reduced by the reduction of its intrinsic dissolved oxygen value.Can be in the case of in not adding other chemical substance to hot-water heating system in the situation that or in conjunction with such removing of carrying out chemical substance in adding other chemical substance to hot-water heating system.
In another embodiment of the present invention, can or separately or add/remove in conjunction with chemistry and regulate or meet measured ORP by the non-chemically technology of at least one systematic parameter of change.By adding technique non-chemically, can affect the ORP in any one actual zone (or link zone), the upstream of ORP control zone.Representational non-chemically technology and systematic parameter comprise feed pump or the condenser pump of for example selecting particular type; The subregion that system is processed stream flows; Mixed or combination is flowed; The speed of selecting the material of the structure of the each several part of hot-water heating system to be oxidized with control; Cathodic protection; Electromagnetic wave produces; Physical property changes; Analog; With its combination.
Can understand better aforementioned content by reference to example below, it is intended to for exemplary object and the scope that is not intended to the application that limits the present invention or its any mode.
Example 1
Fig. 1 has described the hot-water heating system of 3 assemblies of simplifying.Makeup water stream is through " oxygen-eliminating device ", " FW pump " and enter " boiler ".Described boiler and then generation are used to various downstream " useful steam ".In this example, can in Fig. 1, be denoted as the FW pump discharge place that is denoted as " 2 " in the oxygen-eliminating device outlet of " 1 " or Fig. 1 and monitor/control ORP.Can make a response to REDOX Stress in real time, because its independent generation in oxygen-eliminating device and/or FW pump.After FW pump after oxygen-eliminating device and/or for how concrete corrosion control, active chemistry also can be fed in oxygen-eliminating device.
Example 2
Fig. 2 illustrates more complicated boiler configuration, comprises multiple feed pumps, multiple heat exchanger and steam generator (, boiler).In such configuration, can use condenser, heat exchanger, pump, boiler, the application of processing steam of any number (, one, two or more) etc.In Fig. 2, in the time that mobile feedwater is moved to " processing the use of steam " region 1 and 2, it is shown as solid arrow line.In the time that condensed steam is fed to the various shop equipments position of the shell-side that can comprise heat exchanger or directly turns back to condenser zone, it is shown as empty arrow line.If desired, can be used as blowdown makes not meet for the condensed water of the shop equipment water specification of boiler feedwater and leaves system.
Wherein can monitor/control the position of ORP and/or be denoted as Fig. 2 " 22 " for the example of the supplying position of active chemistry.The location that such user controls is allowed for local corrosion protective capability and the overall corrosion protection of the group of concrete unit and/or unit.
Example 3
Fig. 3 described ORP arrange can be how for the system of different temperatures and different.Temperature shown in Fig. 3 can typical example as the different operation protection/control zone in different shop equipments or same facility equipment.In this example, ORP arranges the ORP setting range of selecting a series of scopes of the vertical line from being depicted as sign " preferably ", " broader ", " the broadest ".Depend on the accuracy (, performance constraint) of the equipment in shop equipment, available ORP setting range or point can change.That is to say, some shop equipments can be processed narrow or preferred ORP setting range, and other shop equipment only can be processed broader ORP setting range.
Relative with the reference electrode (being designated as " EPBRE " in Fig. 3) of external pressure balance with 0.1 normality (normal) potassium chloride packing fluid, typically will record T ORP number.Can be by being positioned at " heat exchanger 2 " in feedwater (Fig. 2) T ORP probe measurement afterwards and control the one 180 °F of control zone, and active chemistry immediately " condenser " in feedwater (Fig. 2) be fed to afterwards in feedwater.
Can be by being positioned at " heat exchanger 3 " in feedwater (Fig. 2) T ORP probe measurement afterwards and control the 2 350 °F of control zone, and active chemistry immediately " heat exchanger 3 " in feedwater (Fig. 2) be fed to before in feedwater.
Can be by being positioned at " heat exchanger 4 " in feedwater (Fig. 2) T ORP probe measurement afterwards and control the 3 500 °F of control zone, and active chemistry immediately " heat exchanger 4 " in feedwater (Fig. 2) be fed to before in feedwater.
Example 4
This example view at the multiple REDOX active materials of position feeding to control the T ORP of single position, as shown in Figure 4.Control T ORP probe and be directly placed on the upstream for the supplying position of REDOX active material #2.T ORP probe was used to measure T ORP before the feeding of REDOX active material #2.Then, switching T ORP pops one's head in to control the feeding of another REDOX active material (#1) of the upstream that is fed in single T ORP probe.It should be noted that, in the time that (manually controlling) REDOX active material (#2) is cut off, this loss affect rapid permeability shop equipment hydrochemical compositions and by T ORP probe sensing.Controller (in this example, controller is automation for REDOX active material (#1)) is initiated the additional feed of REDOX active material #1 immediately, to supplement the breach of REDOX active material #2.
The controlled feeding of REDOX active material #1 can reach and maintain T ORP and arrange, and has therefore minimized the corrosion in heat exchanger during this event.Note, once REDOX active material #2 manually gets back to and opens, compensate corrosion control equipment (, T ORP probe system) to maintain the desired T ORP setting for corrosion control by cutting off the feeding of REDOX active material #1 immediately.
Example 5
This example view the T ORP of direct measurement corrosion event tMhow the uncertain response of probe and in real time ORP measurement result serve as the direct indicator from the corrosion in the hot-water heating system of REDOX Stress event.
T ORP probe is made a response to the formation of the corrosion product in FW.REDOX in FW stress comprise that for example the complicated conjugate ion corrosion as Fe2+/Fe3+ or Cu+/Cu2+ is right.In all iron-based FW heaters, the water of high DO (, being greater than 500ppb) starts to enter FW heater.The room temperature ORP at calorifier inlets place and in real time ORP be respectively at first-125mV and-280mV.Once the REDOX stress event that experience is added, the room temperature ORP at calorifier inlets place and in real time rise to respectively-70mV of ORP and-30mV.The sensitivity of T ORP probe (ORP increases 250mV in real time) is clearly regarded as comparing with room temperature ORP probe (only having increased 55mV).FW heater outlet place in real time and room temperature ORP probe be respectively at first-540mV and-280mV.After high REDOX stress event, FW heater outlet place in real time and room temperature ORP probe become respectively-140 with-280mV.Notice real-time ORP rising 400mV and room temperature ORP shows that it is important not changing.
Be not intended to be limited to any special theory; But the room temperature ORP measurement result in the exit of FW heater shows that the theory not changing is that the DO that exits FW heater runs through DO in the porch of FW heater (ingress) event that enters keeps not changing.The corrosion that the reason that in real time ORP number so sharply rises at FW heater outlet place has occurred in most likely due to FW heater self.This event generation T ORP probe detects the sufficient supplies of the undetected ionic oxide formation iron substance material but room temperature ORP pops one's head in.
Stride across wherein and see identical impact at the copper base FW of FW heater internal consumption dissolved oxygen heater.Again, room temperature ORP measurement result does not show and changes in the exit of FW heater, and T ORP sonde response demonstrates the number of rising, this is because cupric oxide ionic species material (conjugate pair) is released in FW and exits FW heater, is not only that room temperature ORP instrument is sensed by T ORP probe.
Example 6-non-chemically technology
Following paragraph provides the several examples that change the non-chemically technology that can be used to the systematic parameter of controlling the measured ORP in hot-water heating system.Those skilled in the art can utilize these technology in the case of there is no the experiment of many degree.
Pump is selected: pump for air enters, can be famously bad actor (usually impact) undesirably and can add-on system in redox stress.Depend on and expect such eliminating that enters or expect on the contrary it, the selection of feed pump or condenser pump type can affect ORP measurement result quite significantly.For example, be all spectra that possible inefficacy and air enter such as the pump design parameter of piston packaging, check-valves, barrier film, sealing, follower, impeller etc.Air enters the lower pressure side that typically occurs in pump during the attraction stage of pumping.
Subregion: can be only to vapor stream with quantitatively carry out subregion and make some or part system flow turn to many devices via by-pass flow, described device can affect intrinsic ORP and it is turned back to main system stream.For example, electrochemistry ionization process can be used to affect its chemical property and therefore affect the ORP character in by-pass flow.
Mixed: to there is the system of different ORP character or process stream and can be mixed in and come together to affect ORP and therefore affect the corrosion of down-stream system with known/controlled/ratio of calculating.
Material: the part of the separation of the system of being made up of different materials can affect ORP, and can comprise and use corrosion property to reach the expectation ORP for hot-water heating system with particular combinations.For example, have for the good affinity of dissolved oxygen with by oxidation under in check speed local reduce process the dissolved oxygen value in water material (for example, any material that can be oxidized on one's own initiative, such as aluminium, chromium, analog and its combination, and even, more the material of multiple reactionness will be lithium, sodium, magnesium, zinc, analog and its combination).Subsequently, in processing, water then by have lower ORP value and reduce tendentiousness with corrosion then by other material of being protected preferably.Except whole district or whole equipment in this case may be to prevent that district subsequently from avoiding the anode region of corrosion strength, this is similar to anodic protection to a certain extent.The material (for example, hardware or system unit) that adds one or more ORP impact at the upstream end in the district from subsequently, described district subsequently requires the concrete ORP number for corrosion protection.Although described many hardware are generally considered to be metal, they need not be metal.For example, activated carbon may prove effective chemistry change material, and is also therefore ORP change material.
Cathodic protection: be similar to applying electric current and can being used to change ORP space of cathodic protection, each several part or region that water is processed in contact that wherein can cathodic protection equipment.In an extreme case, can apply electrochemical voltage operation cathodic protection to introduce chemistry change material, such as hydrogen with sufficiently high.Then hydrogen will reduce ORP value and can combine to reduce measured ORP value with oxygen part (or downstream) in it self.
Electromagnetic wave: in the region that many devices can produce at electromagnetic wave, such as light source, ultraviolet ray add, microwave induced ripple etc., with and combination.Electromagnetic wave source can be such as connecting continuously or off and on in check mode, pulse etc.Wave source can be used to affect directly or indirectly ORP material in any region via their specific function.For example, UV light can activate reacting of cobalt catalysis between the sulphite in oxygen and water.
Can not according to too much experiment of the present disclosure in the situation that, make and carry out disclosed herein and require all compositions and the method for patent protection.Although can specialize in many different forms the present invention, describe concrete preferred embodiment of the present invention herein in detail.The disclosure is the example of principle of the present invention and is not intended to the present invention to be limited to illustrated specific embodiment.In addition, unless clearly state reverse situation, the use of term " " is intended to comprise " at least one " or " one or more ".For example, " equipment " is intended to comprise " at least one equipment " or " one or more equipment ".
Or be intended to comprise these two with absolute term or to be similar to given any scope, and any definition using is intended to clarification unrestricted herein.Although setting forth number range and the parameter setting of the scope of broadness of the present invention is approximation, as far as possible accurately report the numerical value of setting forth in concrete example.But any numerical value comprises inevitable some error being caused by the standard deviation finding in their corresponding thermometrically results inherently.In addition, all scopes disclosed herein should be understood to comprise any and all subranges (comprising all marks and whole value) that are wherein included into.
In addition, the present invention comprises the some or all any and all possible combination in each embodiment described herein.Other reference of recording in any and all patents, patent application, scientific paper and this application and any reference of wherein recording are integrated with herein by reference with their entirety.It is also to be understood that, the various changes to the preferred embodiment of describing at present herein and amendment will be obvious for a person skilled in the art.Can make such change and amendment and not depart from the spirit and scope of the present invention and do not weaken the advantage of its expection.Therefore, expect that the claim that such change and amendment are enclosed covers.

Claims (24)

1. control real-time oxidation-reduction potential ORP in hot-water heating system to reduce a method for the corrosion in described hot-water heating system, described method comprises:
(a) limit the one or more operation protections district (" zone " or " zones ") in described hot-water heating system;
(b) select at least two in described restriction district, at least two in wherein said selection district comprise that at least one ORP that can operate to measure described real-time ORP and communicate by letter with controller pops one's head in;
(c) when described hot-water heating system is during in operating temperature and pressure, intermittently or measure continuously the described real-time ORP at the one or more places in described selection district;
(d) measured real-time ORP is sent to described controller;
(e) assessment is that measured real-time ORP or the ORP of the calculating of the real-time ORP based on measured meet ORP setting, and wherein said ORP setting is to arrange or arrange for the different ORP of at least two in described selection district for the identical ORP of each of described selection district;
(f) if not meeting described ORP, measured real-time ORP or the ORP that calculates arrange, carry out so at least one in action below: (i) one or more active chemistries of effective dose are fed in described hot-water heating system, (ii) remove one or more active chemistries of effective dose from described hot-water heating system, and (iii) change systematic parameter; And
(g), after trigger event, from described selection district ramps up to another in described selection district alternatively.
2. method according to claim 1, wherein said ORP probe comprises Temperature Detector, noble metal electrode and reference electrode.
3. method according to claim 1, wherein said trigger event is based on timetable.
4. method according to claim 1, at least one in wherein said selection district is in monitoring and/or alarm mode, and at least one selects district in control model.
5. method according to claim 4, at least one in wherein said selection district can manually or automatically be switched between monitoring and/or alarm mode and control model.
6. method according to claim 1, wherein said ORP arranges and changes in time.
7. method according to claim 1, comprises and determines with first and select the corresponding ORP in district to arrange, and determines alternatively and additional ORP setting that additional selection district is corresponding.
8. method according to claim 7, comprises and determines that independently a described ORP arranges and/or determines that independently the each additional ORP corresponding with each additional selection district arranges.
9. method according to claim 1, comprises that the performance constraint based on described hot-water heating system is identified for the ORP setting in each selection district independently.
10. method according to claim 1, wherein from comprising described in the group selection of the following that ORP arranges: the ORP set point of selecting from one or more single values and the ORP setting range from one or more scopes selections of value.
11. methods according to claim 1, comprise if described the first real-time ORP of measurement or the first calculating ORP based on the real-time ORP of the first measurement do not meet for the ORP in the first selection district to be arranged, measure so described first and select the first real-time ORP in district and select district to carry out at least one in described action to described first; If and/or described first measure real-time ORP or described first calculate ORP do not meet for described first select district ORP arrange, measure so the described first real-time ORP and one or more other selection places of district carry out one of described action; And/or one or more places in described selection district measure one or more in one or more real-time ORP and the real-time ORP based on measured, calculate for one or more other and select one or more other real-time ORP in districts.
12. methods according to claim 1, wherein measured real-time ORP or the ORP instruction of calculating are corresponding selects in district or another selects the amount of the electroactive substance in district; And/or wherein in measured real-time ORP or the ORP instruction corresponding selection of the remote-effects district calculated or another select the amount of the chemicals of the amount of the electroactive substance in district.
13. methods according to claim 12, wherein said electroactive substance directly affects described real-time ORP.
14. methods according to claim 1, comprise automatically and/or manually carry out at least one in described action.
15. methods according to claim 1, wherein from comprising active chemistry described in the group selection of the following: oxidant, reducing agent, corrosion inhibitor, corrosive agent and its combination.
16. methods according to claim 1, comprise by method described in network operation.
17. methods according to claim 16, wherein said network is internet.
18. 1 kinds have the digital storage media of computer executable instructions stored thereon, and described instruction can operate to execute claims the method described in 1.
19. methods according to claim 1, wherein from comprising hot-water heating system described in the group selection of the following: fossil fuel burning water pipe or multitubular boiler; Hot-water heater; Heat exchanger; Steam generator; Comprise the nuclear energy power system of light-water reactor, pressurized water reactor and boiling water reactor; Boats and ships unit; Internal combustion engine and diesel engine cooling system; Evaporator system; Hot desalting system; Evaporator system; Comprise the papermaking operation of slurrying processing and bleaching; Wafer polishing and planarization; Burning gases discharge; Fermentation process; Ground heat treatment; The reduction of water-based organic oxidation is synthetic; Polymerization processing; Steam jet equipment; Process operation; Be attached to these auxiliary equipment.
20. methods according to claim 1, comprise the oxygen that removes effective dose from described hot-water heating system.
21. methods according to claim 20, also comprise and use gas-permeable membrane to remove described oxygen.
22. methods according to claim 20, also comprise and use oxygen-eliminating device to remove described oxygen.
23. methods according to claim 1, wherein change systematic parameter and comprise at least one that select in action below: select specific chemicals feed pump design; Select specific condenser pump design; Subregion vapor flow and quantitative; There is the system of different ORP character or process stream so that controlled ratio is mixed; Select the structure material for operation protection district based on the compatibility for dissolved oxygen; Apply electric current so that cathodic protection to be provided; Introduce electromagnetic wave; Regulate physical property; With and combination.
24. 1 kinds for operating the corrosion control equipment of the hot-water heating system that realizes method according to claim 1; described hot-water heating system has multiple operation protections district (" zone " or " zones "); at least two in wherein said district is to select district, and described equipment comprises:
Receiver, it is communicated by letter with one or more oxidation-reduction potential ORP probes, activate the subset of described ORP probe, the ORP probe of each activation can operate to measure the real-time ORP at operating temperature and pressure place, and at least two at least one that comprise in described ORP probe in described selection district;
Processor, it can operate to resolve the measured real-time ORP that is delivered to described receiver from the ORP probe of each activation, and wherein said processor is directly resolved measured real-time ORP or is resolved the ORP that the real-time ORP based on measured calculates; And
Conveyer, it is introduced described hot-water heating system by one or more active chemistries and communicates by letter with the feed apparatus that affects described real-time ORP and change with can operate to manage, if the real-time ORP wherein resolving does not meet ORP and arranges, so described processor can operate to send output signal to described feed apparatus by described conveyer.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113189143A (en) * 2015-01-12 2021-07-30 艺康美国股份有限公司 Apparatus, system, and method for maintaining sensor accuracy
CN113348365A (en) * 2018-11-27 2021-09-03 凯米拉公司 Method for estimating gas phase corrosion load

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITUB20155513A1 (en) * 2015-11-12 2017-05-12 Gel Srl KIT FOR PROTECTION AND CONTEMPORARY REMOVAL OF METALLIC OXIDES FROM A CLOSED CIRCUIT HEATING SYSTEM.
CN105300167B (en) * 2015-12-11 2017-11-03 王耀红 A kind of wall-hung boiler cleaning machine
CN113310512B (en) * 2021-05-17 2022-08-09 扬州华大锅炉有限公司 Thermodynamic system corrosion protection on-line detection device for hot water boiler
WO2024089448A1 (en) * 2022-10-25 2024-05-02 Ecospec Noveltech Pte Ltd System and method for in-situ formation of barrier coating on metallic article in contact with or exposed to water within a water system

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0493869A1 (en) * 1991-01-04 1992-07-08 Japan Gore-Tex, Inc. Apparatus for treating water
ES2574005T3 (en) * 2003-11-20 2016-06-14 Nalco Company Method to inhibit corrosion in hot water systems
WO2006073619A2 (en) * 2004-11-30 2006-07-13 Ashland Licensing And Intellectual Property Llc Automated process for inhibiting corrosion in an inactive boiler containing an aqueous system
JP2006274427A (en) * 2005-03-30 2006-10-12 Miura Co Ltd Water treating agent and water treatment method
US8658095B2 (en) * 2007-01-29 2014-02-25 Nalco Company High temperature and pressure oxidation-reduction potential measuring and monitoring device for hot water systems
US8153057B2 (en) * 2007-07-24 2012-04-10 Nalco Company Method and device for preventing corrosion in hot water systems
US8906202B2 (en) * 2007-07-24 2014-12-09 Nalco Company Method of detecting and reducing contamination in papermaking boiler systems
JP2009166010A (en) * 2008-01-21 2009-07-30 Mitsubishi Heavy Ind Ltd Exhaust gas treatment system and its method of coal fired boiler
JP2011110531A (en) * 2009-11-30 2011-06-09 Mitsubishi Heavy Ind Ltd Desalination apparatus and desalination method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113189143A (en) * 2015-01-12 2021-07-30 艺康美国股份有限公司 Apparatus, system, and method for maintaining sensor accuracy
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CN113348365B (en) * 2018-11-27 2023-09-19 凯米拉公司 Method for estimating vapor phase corrosion load

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AR090505A1 (en) 2014-11-19
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AU2013246154A1 (en) 2014-08-28
EP2864714A4 (en) 2016-02-24
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WO2013155036A1 (en) 2013-10-17
TWI641798B (en) 2018-11-21

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