CN115196718A - Circulating cooling water treatment method - Google Patents
Circulating cooling water treatment method Download PDFInfo
- Publication number
- CN115196718A CN115196718A CN202210826874.7A CN202210826874A CN115196718A CN 115196718 A CN115196718 A CN 115196718A CN 202210826874 A CN202210826874 A CN 202210826874A CN 115196718 A CN115196718 A CN 115196718A
- Authority
- CN
- China
- Prior art keywords
- water
- cooling water
- circulating cooling
- ions
- corrosion
- 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
Links
- 239000000498 cooling water Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 150000002500 ions Chemical class 0.000 claims abstract description 31
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 230000005764 inhibitory process Effects 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 9
- 238000005536 corrosion prevention Methods 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 230000007774 longterm Effects 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims description 7
- 239000003814 drug Substances 0.000 claims description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims 1
- 239000003957 anion exchange resin Substances 0.000 claims 1
- 239000003729 cation exchange resin Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 8
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 5
- 239000003899 bactericide agent Substances 0.000 abstract description 5
- 235000015097 nutrients Nutrition 0.000 abstract description 3
- 239000003755 preservative agent Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 229910001410 inorganic ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- -1 Na + Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention belongs to the technical field of circulating cooling water treatment, and the corrosion, scaling and nutrient ions in water are selectively removed through commercial resin to realize the effects of corrosion prevention, scale inhibition and bacteriostasis, so that the water-saving agent not only can be used for replenishing water production of a circulating cooling water system, but also can be used for bypass control of the water quality of the circulating cooling water system, the long-term and stable operation of the circulating cooling water system can be realized without adding preservatives, corrosion inhibitors and bactericides, and the water-saving effect is obviously higher than that of the conventional technology (the concentration multiple reaches 100 or higher, the discharged water amount is less than 1/10 of the conventional technology, and the replenished water amount is less than 1/3 of the conventional technology).
Description
Technical Field
The invention relates to a method for treating circulating cooling water, in particular to a method for controlling the quality of the circulating cooling water by selectively removing corrosion, scale and nutrient ions to realize the effects of corrosion prevention, scale inhibition and bacteriostasis, which can be used for the production of make-up water of a circulating cooling water system and the bypass control of the quality of the circulating cooling water system.
Background
The industrial water generally comprises process water, boiler water, washing water, cooling water and the like, wherein the cooling water accounts for a considerable proportion in the industrial water, and can reach 80% -90% of the total industrial water, so that the utilization rate of the water can be improved by recycling the cooling water, and the aim of saving water resources is fulfilled. The circulating cooling water system uses water as a cooling medium and consists of heat exchange equipment, cooling equipment, a water pump, a pipeline and other related equipment. The inorganic ions in the circulating cooling water are continuously concentrated due to the continuous evaporation of water to easily cause scale formation (together with Ca) 2+ 、Mg 2+ Correlation)Corrosion (with Cl) - 、SO 4 2- Related) and microbial growth (related to N, P, the major limiting factor, mostly PO 4 3- And) the long-term stable operation of the circulating cooling water system is seriously influenced. Therefore, in the daily operation process of the circulating cooling water system, the concentration of the inorganic ions needs to be controlled at a safe level (the concentration multiple is usually 5, and a small amount of cases reach 10) through timely water supplement and drainage, and in addition, corrosion inhibition, scale inhibition and bactericide needs to be frequently added to ensure the stable operation of the system. The related medicament is one of the main contents of the invention patent application of the circulating cooling water system, such as the invention patent with the application number of 202111375148.X and the publication number of CN 114180730A, which is named as a high concentration multiple corrosion and scale inhibitor for the circulating cooling water system and a water treatment method; also, for example, the invention patent with the application number of 201610546025.0 and the publication number of CN 107601684A, which is named as the phosphorus-free composite scale and corrosion inhibitor and the application thereof, and the treatment method of the circulating cooling water, etc. The use of the agents not only increases the running cost of a circulating cooling water system, but also causes secondary pollution and increases the treatment difficulty of the water discharged outside the system.
Since the phenomena of corrosion, scaling and growth of microorganisms in the circulating cooling water system and Ca 2+ 、Mg 2+ 、Cl-、SO 4 2- 、PO 4 3- In connection with (hereinafter referred to as harmful ions), the control of the concentration of these harmful ions from the source can achieve corrosion prevention, scale inhibition and microorganism growth inhibition (hereinafter referred to as bacteriostasis), in contrast to other ions such as Na + 、K + 、CO 3 2- 、HCO 3 - 、SiO 3 2- The circulating cooling water system is not harmful to stable operation (hereinafter referred to as harmless ions), and some ions are even beneficial (recent research shows that NO is not harmful to the running of the circulating cooling water system) 3 - 、CO 3 2- 、HCO 3 - 、HSiO 3 - 、SiO 3 2- Etc. have a general preservative effect). Thus, selective removal of harmful ions from raw water while retaining them (to achieve corrosion protection) is a source to control corrosion and scaling problems, inhibit corrosionThe method is key for controlling the propagation of microorganisms, can realize the stable operation of a circulating cooling water system when no preservative, corrosion inhibitor or bactericide is added, and has very important economic and environmental significance. As a classical ion removal technique, conventional commercial resins can effectively remove these harmful ions, but the greatest disadvantage is the lack of ion selectivity, and the need to exchange all inorganic ions for counter ions, which greatly increases the consumption of counter ions in the regeneration liquid, and the lack of retention of other ions beneficial to the system, which is costly to operate, is common to ensure complete removal of all harmful ions. For example, the invention patent with application number of 200810196877.7 and publication number of CN 101353190A is named as a method for ion exchange softening micro-alkalization treatment of circulating cooling water, and Na-type cation resin is adopted to carry out Ca treatment on water 2+ 、Mg 2+ Total exchange of plasma for Na + Ionic, then OH form, CO 3 2- Form or HCO 3 - Anionic resin for removing Cl in water - 、SO 4 2- All anions are exchanged into OH-and CO 3 2- Or HCO 3 - The finally prepared circulating cooling water is single NaOH and Na in fact 2 CO 3 Or NaHCO 3 And (3) solution. At present, a reverse osmosis system is widely adopted as a final treatment unit in industrial practice of a circulating cooling water system to produce deionized water with extremely low salinity as make-up water (all ions are indiscriminately removed), the process has high operation cost and is easy to generate a large amount of strong brine which is difficult to treat, such as the invention patent with the application number of 201811637093.3 and the publication number of CN 109502853A and the name of the invention patent of a reclaimed water treatment system for circulating cooling water of a power plant, and the like. Part of the invention patents adopt electrochemical process to produce the make-up water of the circulating cooling water system, wherein high-concentration OH is formed near the cathode - Promote the crystallization and precipitation of the scale ions, and the oxygen and oxygen free radicals generated by the electrolysis of water near the anode are combined to form hydrogen peroxide and ozone, thereby forming the sterilization effect. For example, the invention is named as an invention patent of a circulating cooling water bypass water treatment system and a bypass water treatment method, with the application number of 201610388112.8 and the publication number of CN 105800842A; also disclosed is application No. 202111639580.5 and publication No. CN 114249387A, entitled "article for referenceThe invention relates to a method for treating circulating cooling water by self-coupling inverted-electrode descale of a deposition electrode. However, the electrochemical process mainly achieves the goals of scale inhibition and sterilization, and has no anticorrosion function.
Disclosure of Invention
The invention provides a method for controlling the quality of circulating cooling water by selectively removing harmful ions in water, which has obvious corrosion prevention, scale inhibition and bacteriostasis effects, can realize long-term and stable operation of a circulating cooling water system without adding preservatives, corrosion inhibitors and bactericides, and has a water-saving effect which is obviously higher than that of the conventional technology (the concentration multiple reaches 100 or higher, the external water discharge amount is less than 1/10 of the conventional technology, and the supplementary water amount is less than 1/3 of the conventional technology).
The invention is characterized in that: it adopts a special mode to activate the traditional commercial resin, so that the ion exchange reaction range is limited to the harmful ion Ca 2+ 、Mg 2+ 、Cl-、SO 4 2- 、PO 4 3- (thus avoiding problems of corrosion, scaling, microbial growth), while Na in water + 、K + 、CO 3 2- 、HCO 3 - 、SiO 3 2- The harmless ions remain in the circulating cooling water (and contribute to corrosion protection) because they do not participate in the ion exchange reaction. The method can be used for producing qualified system make-up water and can also be used for bypass treatment to ensure the water quality of the system.
Compared with the prior art, the technology has the following advantages:
(1) The effects of corrosion prevention, scale formation and bacteria inhibition of the circulating cooling water system are realized through source water quality control.
(2) The circulating cooling water system has no corrosion prevention, scale inhibition and bactericide addition during long-term operation, and the water-saving potential is obviously higher than that of the conventional technology.
Detailed Description
The working principle and the implementation mode of the invention are explained in detail as follows:
1. the invention relates to a circulating cooling water treatment method, which has the following principle:
the method for treating the circulating cooling water adopts regeneration containing harmless ionsThe solution activates conventional commercial resins to pre-load these non-deleterious ions onto the resin, ultimately inhibiting their ion exchange reaction during the ion exchange process (i.e., these non-deleterious ions do not participate in the ion exchange reaction and remain in the water). At the same time, harmful ion Ca 2+ 、Mg 2+ 、Cl - 、SO 4 2- 、PO 4 3- The ion exchange reaction is not affected (i.e. the harmful ions are separated from the water after completing the ion exchange reaction). The special activation mode does not change the physicochemical properties (such as space tension and distance between exchange sites) of the traditional commercial resin, and does not enhance the ion exchange capacity of the resin for target ions (only inhibits the ion exchange capacity of harmless ions), and the phenomenon finally shows that the traditional commercial resin after being activated by the special mode selectively removes the harmful ions such as corrosion, scale formation, nutrient ions and the like in water.
2. The embodiment of the method for treating the circulating cooling water comprises the following steps:
firstly, according to the harmless ion type in the raw water discovered by research, adding different harmless ions into the regenerated liquid to activate the traditional commercial anion and cation resins in advance, then starting normal ion exchange reaction, feeding the raw water from water inlet main pipe, respectively flowing into cation resin unit and anion resin unit, respectively and selectively removing Ca in the raw water 2+ 、Mg 2+ (Anode column) and SO 4 2- 、PO 4 3- 、Cl - (cathode column), and the effluent is converged to the effluent main pipe.
Example 1
The reclaimed water of a certain thermal power plant can be used as the water supplement of the circulating cooling water after being treated by the method. And (3) respectively introducing the reclaimed water into a cation selective removal unit and an anion selective removal unit, continuously adsorbing for 24h, and regenerating the selective material every 2 days. Ca in the effluent 2+ 、Mg 2+ 、SO 4 2- 、Cl - The removal rates of (a) are 70%, 85%, 80% and 50% or more, respectively.
Example 2
Circulation cooling of central air-conditioning system of certain libraryWater respectively enters a cation selective removal unit and an anion selective removal unit, the continuous adsorption is carried out for 14h, the selective material is regenerated every 5 days, and Ca in the effluent water 2+ 、Mg 2+ 、SO 4 2- 、Cl - The removal rates of (a) are 80%, 75% and 60% or more, respectively.
Example 3
Cooling water in a circulating cooling water system of a fertilizer plant enters a cation selective removal unit and an anion selective removal unit respectively, the absorption is continuously carried out for 20 hours, selective materials are regenerated every 3 days, and Ca in the effluent water 2+ 、Mg 2+ 、SO 4 2- 、PO 4 3- 、Cl - The removal rates of (a) are 80%, 75%, 85%, 90% and 50% or more, respectively.
Claims (2)
1. A method for treating circulating cooling water is characterized in that: it adopts anion and cation exchange resin to selectively remove Ca in water 2+ 、Mg 2+ 、Cl-、SO 4 2- 、PO 4 3- And the corrosion inhibitor has no removal effect on other ions, and realizes the long-term corrosion prevention, scale inhibition and bacteriostasis effects of the circulating cooling water system under the condition of no medicament addition.
2. The method for treating recirculated cooling water according to claim 1, wherein: the circulating cooling water treatment method can be used for producing qualified system make-up water and can also be used for bypass treatment to ensure the water quality of a system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210826874.7A CN115196718A (en) | 2022-07-13 | 2022-07-13 | Circulating cooling water treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210826874.7A CN115196718A (en) | 2022-07-13 | 2022-07-13 | Circulating cooling water treatment method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115196718A true CN115196718A (en) | 2022-10-18 |
Family
ID=83579794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210826874.7A Pending CN115196718A (en) | 2022-07-13 | 2022-07-13 | Circulating cooling water treatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115196718A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001096281A (en) * | 1999-09-29 | 2001-04-10 | Nippon Rensui Co Ltd | Method of recovering desalted water from fluorine- containing waste water |
| JP2001246377A (en) * | 2000-03-06 | 2001-09-11 | Japan Organo Co Ltd | Operating method of condensate demineralizer |
| US20030196962A1 (en) * | 2002-04-22 | 2003-10-23 | William Fries | Process for selective removal of toxic ions from water |
| US20080251461A1 (en) * | 2007-04-16 | 2008-10-16 | Parker Garth R | Water treatment process |
| CN101353190A (en) * | 2008-09-05 | 2009-01-28 | 武汉大学 | Recirculated cooling water ion exchange softening micro-basification processing method |
| CA2745089A1 (en) * | 2008-12-03 | 2010-06-10 | Hydroionic Technologies Co. Ltd. | System and method for wastewater treatment |
| CN101898813A (en) * | 2010-07-23 | 2010-12-01 | 中国神华能源股份有限公司 | Method of cold water treatment in generator |
| CN101920215A (en) * | 2010-07-23 | 2010-12-22 | 中国神华能源股份有限公司 | Mixed resin and preparation method thereof |
| US20120189513A1 (en) * | 2011-01-20 | 2012-07-26 | Gordon Rossiter | Ionic impurities rejection and chromatographic purification using ion exchange |
| JP2015199050A (en) * | 2014-04-10 | 2015-11-12 | 三菱レイヨンアクア・ソリューションズ株式会社 | Method of removing metal ion in saturated salt water |
| JP6513250B1 (en) * | 2018-03-28 | 2019-05-15 | 大阪瓦斯株式会社 | Ion exchange device |
-
2022
- 2022-07-13 CN CN202210826874.7A patent/CN115196718A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001096281A (en) * | 1999-09-29 | 2001-04-10 | Nippon Rensui Co Ltd | Method of recovering desalted water from fluorine- containing waste water |
| JP2001246377A (en) * | 2000-03-06 | 2001-09-11 | Japan Organo Co Ltd | Operating method of condensate demineralizer |
| US20030196962A1 (en) * | 2002-04-22 | 2003-10-23 | William Fries | Process for selective removal of toxic ions from water |
| US20080251461A1 (en) * | 2007-04-16 | 2008-10-16 | Parker Garth R | Water treatment process |
| CN101353190A (en) * | 2008-09-05 | 2009-01-28 | 武汉大学 | Recirculated cooling water ion exchange softening micro-basification processing method |
| CA2745089A1 (en) * | 2008-12-03 | 2010-06-10 | Hydroionic Technologies Co. Ltd. | System and method for wastewater treatment |
| CN102355933A (en) * | 2008-12-03 | 2012-02-15 | 海卓恩克科技有限公司 | System and method for wastewater treatment |
| CN101898813A (en) * | 2010-07-23 | 2010-12-01 | 中国神华能源股份有限公司 | Method of cold water treatment in generator |
| CN101920215A (en) * | 2010-07-23 | 2010-12-22 | 中国神华能源股份有限公司 | Mixed resin and preparation method thereof |
| US20120189513A1 (en) * | 2011-01-20 | 2012-07-26 | Gordon Rossiter | Ionic impurities rejection and chromatographic purification using ion exchange |
| JP2015199050A (en) * | 2014-04-10 | 2015-11-12 | 三菱レイヨンアクア・ソリューションズ株式会社 | Method of removing metal ion in saturated salt water |
| JP6513250B1 (en) * | 2018-03-28 | 2019-05-15 | 大阪瓦斯株式会社 | Ion exchange device |
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Application publication date: 20221018 |