CN101898812A - Method for processing generator inner cooling water - Google Patents
Method for processing generator inner cooling water Download PDFInfo
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- CN101898812A CN101898812A CN 201010238528 CN201010238528A CN101898812A CN 101898812 A CN101898812 A CN 101898812A CN 201010238528 CN201010238528 CN 201010238528 CN 201010238528 A CN201010238528 A CN 201010238528A CN 101898812 A CN101898812 A CN 101898812A
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- China
- Prior art keywords
- exchange resin
- ion exchange
- type ion
- cooling water
- inner cooling
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- 239000000498 cooling water Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 55
- 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 abstract description 303
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 303
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 303
- 238000005342 ion exchange Methods 0.000 claims description 86
- 239000011347 resin Substances 0.000 claims description 63
- 229920005989 resin Polymers 0.000 claims description 63
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 230000002411 adverse Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 84
- 239000011734 sodium Substances 0.000 description 75
- 238000002360 preparation method Methods 0.000 description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000007599 discharging Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000010612 desalination reaction Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000002203 pretreatment Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- JSAIENUMNDAGTD-UHFFFAOYSA-N benzene ethene styrene Chemical compound C1=CC=CC=C1.C=C.C=C.C=CC1=CC=CC=C1 JSAIENUMNDAGTD-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 108020004999 messenger RNA Proteins 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Abstract
The invention provides a method for processing generator inner cooling water, which comprises the following steps: contacting generator inner cooling water with ion exchange resin, wherein the ion exchange resin contains OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and the OH type ion exchange resin, the Na type ion exchange resin and the H type ion exchange resin are respectively gel-type ion exchange resin. When the method is used for processing the generator inner cooling water, the pH value of the generator inner cooling water can be kept above 7.5 for a long time, and the method can not produce adverse effect on the electric conductivity of the generator inner cooling water and can keep the electric conductivity of the generator inner cooling water below 1.5 mu S/cm for a long time without corroding the inner components of the generator.
Description
Technical field
The present invention relates to a kind of treatment process of electric generator inner cooling water.
Background technology
Generator is transformed into heat energy owing to energy expenditure with portion of energy in operation process, make the temperature of parts such as rotor, stator raise, and then the winding that causes insulating is aging, the decline of exerting oneself, even burn motor.Therefore, be necessary the parts in the generator are cooled off.But, because electric generator inner cooling water is to work under the environment of high-voltage electric field, therefore, to compare with common water coolant, electric generator inner cooling water also should have good electrical insulation properties except the requirement that will satisfy burn into non-scaling not.Yet the oxygen in the working process of electric generator inner cooling water in the inevitable meeting dissolved air, carbonic acid gas etc. make the pH value of electric generator inner cooling water reduce gradually, and then corrode inner initiation of generator.Therefore, requiring the dissolved oxygen in the electric generator inner cooling water usually is≤80 μ g/L, and the pH value is 〉=7.0, and specific conductivity is≤2.0 μ S/cm; From the angle of safety, in actual moving process, power plant is controlled to be the pH value of electric generator inner cooling water usually 〉=and 7.5, specific conductivity is controlled to be≤1.5 μ S/cm.
In order to reduce the amount of dissolved oxygen in the electric generator inner cooling water, the pH of electric generator inner cooling water is controlled to be is not less than 7.5, and then prevent that the internal part corrosion of generator, power station from using condensed water that water vapor condensation forms the later on inner cold water as generator usually.But, because condensed water is regulated the pH value by adding ammonia, therefore, when the pH of condensed water value is higher (, when the ammonia content in the condensed water is higher), can cause electric conductivity of inside cold water to exceed standard on the one hand; On the other hand, because the material of the stator bar of generator inside is generally copper, and copper is very responsive to ammonia, therefore very easily causes the corrosion of copper.
To sum up, how well the pH value of electric generator inner cooling water is controlled to be and is not less than 7.5, can not significantly improve the specific conductivity of electric generator inner cooling water again, also can not produce corrosion simultaneously and remain a problem demanding prompt solution the generator internal part.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of treatment process of electric generator inner cooling water is provided, this method not only can be for a long time be controlled to be the pH value of electric generator inner cooling water more than 7.5, and can the specific conductivity of electric generator inner cooling water not had a negative impact, the specific conductivity of electric generator inner cooling water can be controlled to be and not be higher than 1.5 μ S/cm, also can not produce corrosion simultaneously the internal part of generator.
The present inventor finds in practice process, although adopting the hybrid resin that is made of OH type ion exchange resin and Na type ion exchange resin handles and the pH of electric generator inner cooling water can be remained more than 7.5 electric generator inner cooling water, but the work-ing life of this hybrid resin is shorter, later just can not realize the pH value of electric generator inner cooling water is remained more than 7.5 in 4 months in operation, and the specific conductivity of electric generator inner cooling water also raises gradually with the prolongation of working time, and the specific conductivity of consequently moving electric generator inner cooling water after 4 months just can not satisfy the service requirements that is lower than 1.5 μ S/cm.
The present inventor finds through repetition test, if employing contains the hybrid resin of OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin then can overcome the problems referred to above simultaneously, can in long time, make the pH value of electric generator inner cooling water and specific conductivity all satisfy service requirements simultaneously.Finished the present invention thus.
The invention provides a kind of treatment process of electric generator inner cooling water, this method comprises electric generator inner cooling water is contacted with ion exchange resin, wherein, described ion exchange resin is the hybrid resin that contains OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and described OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin gel-type ion-exchange resin of respectively doing for oneself.
Contain OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin according to the employed hybrid resin of the treatment process of electric generator inner cooling water of the present invention.In the generator operation process, above-mentioned three kinds of ion exchange resin can be respectively with electric generator inner cooling water in ion following reaction takes place:
nRH+A
n+＝R
nA+nH
+，
mRNa+A
m+＝R
mA+mNa
+，
kR′OH+B
k-＝R′
kB+kOH
-。
The product of above-mentioned ion exchange reaction can continue to take place following reaction, finally generates water and sodium hydroxide, thereby prevents that the prolongation pH value with the generator operation time reduces electric generator inner cooling water gradually owing to dissolved oxygen, carbonic acid gas etc.,
H
++OH
-＝H
2O，
Na
++OH
-＝NaOH。
Adopt method provided by the invention that electric generator inner cooling water is handled, can remain the pH value of electric generator inner cooling water more than 7.5 for a long time on the one hand, also can the specific conductivity of electric generator inner cooling water not had a negative impact on the other hand, can be for a long time the specific conductivity of electric generator inner cooling water be remained below the 1.5 μ S/cm, also can not corrode the internal part of generator simultaneously.
Embodiment
The invention provides a kind of treatment process of electric generator inner cooling water, this method comprises electric generator inner cooling water is contacted with ion exchange resin, wherein, described ion exchange resin is the hybrid resin that contains OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and described OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin gel-type ion-exchange resin of respectively doing for oneself.
The method according to this invention, described ion exchange resin is the hybrid resin that contains OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, above-mentioned three kinds of ion exchange resin act synergistically, and can significantly improve the pH value of electric generator inner cooling water.Wherein, described OH type ion exchange resin can with the negatively charged ion generation ion exchange reaction in the electric generator inner cooling water, Na type ion exchange resin and H type ion exchange resin then can be respectively with electric generator inner cooling water in positively charged ion generation ion exchange reaction, further reaction between the product of above-mentioned ion exchange reaction, thereby the final sodium hydroxide that generates in electric generator inner cooling water has avoided electric generator inner cooling water in the course of the work owing to the pH value that dissolved oxygen, carbonic acid gas etc. causes reduces.
The method according to this invention, described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin are preferably gel-type ion-exchange resin separately.Adopt gel-type ion-exchange resin can be better with electric generator inner cooling water in mineral ion carry out ion-exchange, and then better the pH of electric generator inner cooling water is remained more than 7.5, and can the specific conductivity of electric generator inner cooling water not had a negative impact.Among the present invention, described gel-type ion-exchange resin is meant that inside does not have pore under dry situation, and swollen when suction is at the ion exchange resin of the very fine hole of macromolecular chain internode formation.
The present invention is not particularly limited for the matrix resin of described gel-type ion-exchange resin.Preferably, described gel-type ion-exchange resin is the polystyrene gel-type ion-exchange resin.For example, the matrix resin of described polystyrene gel-type ion-exchange resin can be styrene diethylene benzene copoly mer, and the degree of crosslinking of this multipolymer can be 4-8 mole %.
The method according to this invention, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin can be in very big range.The present inventor finds in experimentation, ion-exchange group in described OH type ion exchange resin, the mol ratio of the ion-exchange group in ion-exchange group in the Na type ion exchange resin and the H type ion exchange resin is 1: 0.1-0.8: 0.08-0.75, and described OH type ion exchange resin, when Na type ion exchange resin and H type ion exchange resin are respectively done for oneself gel-type ion-exchange resin, not only can make the pH value of electric generator inner cooling water remain more than 7.5 for a long time, and can the specific conductivity of electric generator inner cooling water not had a negative impact, specific conductivity can be remained below the 0.5 μ S/cm.
More preferably, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is 1: 0.4-0.75: 0.1-0.45.The mol ratio of the ion-exchange group in described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is within the above-mentioned scope, and when described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin are respectively done for oneself gel-type ion-exchange resin, the pH value of electric generator inner cooling water can be remained for a long time more than 7.5, the specific conductivity of electric generator inner cooling water is remained below the 0.3 μ S/cm.
Further preferably, the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.65-0.75: 0.1-0.2.The mol ratio of the ion-exchange group in described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is within the above-mentioned scope, and when described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin are respectively done for oneself gel-type ion-exchange resin, the pH value of electric generator inner cooling water can be remained on for a long time in the scope of 7.7-8.5, the specific conductivity of electric generator inner cooling water is remained between the 0.1-0.3 μ S/cm.
Most preferably, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is 1: 0.65-0.7: 0.15-0.2, and described OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin gel-type ion-exchange resin of respectively doing for oneself, the pH value of electric generator inner cooling water can be remained 8.5 for a long time like this, the specific conductivity of electric generator inner cooling water is remained 0.27 μ S/cm.
Among the present invention, the quantity of ion-exchange group is meant the quantity that can carry out the ion-exchange group of ion-exchange in the ion exchange resin, can calculate by following formula:
The volume of the operating capacity * ion exchange resin of the quantity of ion-exchange group (mole)=ion exchange resin.
Among the present invention, described operating capacity is meant the mole number according to the ion-exchange group that ion exchange resin contained of the unit volume of the working conditions of DL/T772-2001 regulation and test determines.
The operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin is not particularly limited.For example, the operating capacity of described OH type ion exchange resin can for the 450-600 mmole/liter, the operating capacity of described Na type ion exchange resin and H type ion exchange resin can respectively do for oneself the 950-1010 mmole/liter.Because Na type ion exchange resin can obtain by H type ion exchange resin is made the transition, therefore the operating capacity of described Na type ion exchange resin can be identical with described H type ion exchange resin.The ion exchange resin that operating capacity is in the above-mentioned scope can be commercially available, and for example: described OH type ion exchange resin can be the gel-type ion-exchange resin acquisition of 550A by being purchased from the trade mark of DOW Chemical; Described H type ion exchange resin and Na type ion exchange resin can be the gel-type ion-exchange resin acquisition of 650C by being purchased from the model of DOW Chemical.
The present invention is not particularly limited the content of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, can carry out appropriate selection according to the mol ratio of the ion-exchange group of ion-exchange group in the ion-exchange group in the OH type ion exchange resin in the hybrid resin, the Na type ion exchange resin and H type ion exchange resin and the operating capacity of above-mentioned three kinds of ion exchange resin, not repeat them here.
The method according to this invention, the rate of small round spheres of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin is not particularly limited.From the angle of the physical strength of further raising ion exchange resin, the rate of small round spheres of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin is preferably more than 95% separately.Among the present invention, the coefficient of uniformity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin can be 1.05-1.60 separately, is preferably 1.05-1.40.Among the present invention, described rate of small round spheres is meant that resin is the percentage that the spherical particle number accounts for total number of particles; Described coefficient of uniformity is meant can be by the sieve diameter of 60% volume of resins and the ratio of the sieve diameter of the resin that can pass through 10% volume.
Among the present invention, the ion-exchange group of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin can suitably be selected according to concrete working conditions, is not particularly limited.
Particularly, the ion-exchange group of described OH type ion exchange resin can be quaternary ammonium group, is preferably-N (CH
3)
3OH; The ion-exchange group of described Na type ion exchange resin is preferably-SO
3Na; The ion-exchange group of described H type ion exchange resin is preferably-SO
3The H group.
The hybrid resin that uses in the method according to this invention can adopt this area method preparation commonly used, is not particularly limited.Preferably, described ion exchange resin can prepare by OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin are mixed.
Preferably, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.1-0.8: 0.08-0.75.
More preferably, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.4-0.75: 0.1-0.45.
Further preferably, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.65-0.75: 0.1-0.2.
Most preferably, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.65-0.7: 0.15-0.2.
Usually, the operating capacity of described OH type ion exchange resin can for the 450-600 mmole/liter, the operating capacity of described Na type ion exchange resin and H type ion exchange resin separately can for the 950-1010 mmole/liter.
The volume ratio of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin can be carried out appropriate selection according to the operating capacity of the mol ratio of the ion-exchange group in the OH type ion exchange resin of expection, ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin and selected OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and this paper repeats no more.
Treatment process according to electric generator inner cooling water of the present invention, this method preferably also is included in before the preparation hybrid resin, respectively H type ion exchange resin, Na type ion exchange resin and H type ion exchange resin are carried out pre-treatment, with mechanical impurity and the residual organic that contains in the deionizing exchange resin, simultaneously all right activating ion exchange resin is with the ion-exchange group type of transition for needing of ion exchange resin.The present invention is not particularly limited for described pretreated method, employing well known to a person skilled in the art that method (for example: embodiments of the invention and Comparative Examples are to carry out pretreated with reference to the method for stipulating among the GB/T5476-1996) gets final product, and repeats no more herein.
Because the present invention contains OH type ion exchange resin simultaneously by using, the hybrid resin of Na type ion exchange resin and H type ion exchange resin is realized purpose of the present invention, therefore the present invention is not particularly limited the contact conditions of described electric generator inner cooling water and described ion exchange resin, can carry out described contact under the condition well known to a person skilled in the art, as long as the condition of described contact makes that the pH value of the electric generator inner cooling water after contacting is 7-10, be preferably 7.5-9,7.5-8.5 more preferably, specific conductivity is 0.1-2 μ S/cm, be preferably 0.1-1.5 μ S/cm, more preferably 0.1-0.5 μ S/cm gets final product.Particularly, the time of described contact can for 0.1-2 hour, be preferably 0.1-1 hour.The temperature of described contact is not particularly limited, and can decide with the temperature of the inner inner cold water of exporting of generator, and promptly the inner cold water from the inner output of generator can not cool off or heat up and directly contact with described ion exchange resin.Usually, the temperature of described contact can for 20-80 ℃, be preferably 40-60 ℃.
Can be used for that the generator internal part is carried out the refrigerative inner cold water and handle various according to the treatment process of electric generator inner cooling water of the present invention.Preferably, the pH value that contacts described electric generator inner cooling water before with described ion exchange resin is 5.5-6.5, and specific conductivity is 1-3 μ S/cm.The electric generator inner cooling water that pH value and specific conductivity satisfy above-mentioned requirements for example can carry out the refrigerative condensed water to the generator internal part for being used for.Among the present invention, described condensed water is meant that water vapor is emitted the latent heat of vaporization when temperature is lower than temperature of saturation under its relevant pressure and the liquid water that forms.
Below in conjunction with embodiment the present invention is made a more detailed description.
It is that 868 pH meter is measured the pH value that following examples and Comparative Examples adopt the model that is purchased from Ao Lilong; It is that the conductivitimeter of DDSJ-308A is measured specific conductivity that employing is purchased model from thunder magnetic.
Following examples and Comparative Examples adopt condensed water available from state China Taishan electricity generating corporation, Ltd as electric generator inner cooling water, and before entering the electric generator inner cooling water circulation system, the pH value of this condensed water is 7.5, and specific conductivity is 1.5 μ S/cm.
The de-mineralized water of the flushing ion exchange resin that uses in following examples is available from state China Taishan electricity generating corporation, Ltd, and the pH value is 6.8, and specific conductivity is less than 0.2 μ S/cm.
The OH type ion exchange resin that following examples and Comparative Examples are used is obtained by following negative resin respectively, the H type ion exchange resin that uses is respectively by obtaining with the Xiayang resin, the Na type ion exchange resin that uses will be by being obtained transition by the H type ion exchange resin that obtains with the Xiayang resin respectively, the model of above-mentioned negative resin and positive resin and performance index are shown in the following table 1, wherein, operating capacity is measured according to DL/T772-2001 defined terms and method.
Table 1
Preparation example 1
Adopt following method that positive Resin A is carried out pre-treatment:
The positive Resin A that to rinse well with de-mineralized water is the NaOH solution soaking 8 hours of 5 weight % with the concentration for the twice of this sun resin volume, washes to the transparent clarification of water quality with de-mineralized water then and does not have phenolphthalein alkalinity; Be the HCl solution soaking of 5 weight % after 8 hours with the concentration of twice that is positive resin volume again, wash to the transparent clarification of water quality, drip methyl orange indicator and be yellow and specific conductivity≤1.0 μ S/cm with de-mineralized water.
Preparation example 2
It is Na type ion exchange resin that this preparation example is used for H type ion exchange resin is made the transition.
The H type ion exchange resin that employing is obtained by preparation example 1, with the concentration for the twice of resin volume is the NaOH solution soaking 24 hours of 5 weight %, washing to the transparent clarification of water quality, no phenolphthalein alkalinity and specific conductivity≤1.0 μ S/cm with de-mineralized water then, is Na type ion exchange resin thereby H type ion exchange resin is made the transition.
Preparation example 3
Adopt following method that negative resin B is carried out pre-treatment:
The negative resin B that will rinse well with de-mineralized water is the HCl solution soaking 8 hours of 5 weight % with the concentration for the twice of this negative resin volume, washes to the transparent clarification of water quality, drips methyl orange indicator and be yellow with de-mineralized water then; Be the NaOH solution soaking 8 hours of 5 weight % with the concentration of twice that is the negative resin volume again, wash to the transparent clarification of water quality, no phenolphthalein alkalinity and specific conductivity≤1.0 μ S/cm with de-mineralized water then.
Preparation Comparative Examples 1
Adopt the method identical that positive resin C is carried out pre-treatment with preparation example 1.
Preparation Comparative Examples 2
Adopt the method identical with preparation example 2 that H type ion exchange resin is Na type ion exchange resin transition, different is to adopt the H type ion exchange resin by 1 acquisition of preparation Comparative Examples.
Preparation Comparative Examples 3
Adopt the method identical that negative resin D is carried out pre-treatment with preparation example 3.
Embodiment 1
Present embodiment is used for illustrating the treatment process of electric generator inner cooling water of the present invention.
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains, H type ion exchange resin that preparation example 1 obtains are that 2: 0.5: 0.5 mixed is even according to volume ratio, obtain hybrid resin.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.42: 0.42.
The hybrid resin of preparation is seated in and decides in the cold water ion-exchanger, and the loadings of hybrid resin is 120 liters, then makes de-mineralized water with 3m
3The flow velocity of/h is by this ion exchange resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and specific conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by this ion-exchanger, contact with the ion exchange resin in the ion-exchanger, the time of described contact is 24 minutes, the temperature of contact is 45 ℃, thereby electric generator inner cooling water is handled, electric generator inner cooling water cycle after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, measure the pH value and the specific conductivity of the treated inner cold water of ion-exchanger discharge with pH meter and conductivitimeter, after 1 year as a result, the pH of ion-exchanger water outlet is 7.6, and specific conductivity is 0.14 μ S/cm.
Embodiment 2
Present embodiment is used for illustrating the treatment process of electric generator inner cooling water of the present invention.
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains, H type ion exchange resin that preparation example 1 obtains are that 2: 0.8: 0.2 mixed is even according to volume ratio, obtain hybrid resin.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.67: 0.17.
The hybrid resin of preparation is seated in and decides in the cold water ion-exchanger, and the loadings of hybrid resin is 120 liters, then makes de-mineralized water with 3m
3The flow velocity of/h is by this ion exchange resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and specific conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by in this ion-exchanger, contact with the ion exchange resin in the ion-exchanger, the time of described contact is 24 minutes, the temperature of contact is 45 ℃, thereby electric generator inner cooling water is handled, electric generator inner cooling water cycle after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, measure the pH value and the specific conductivity of the treated inner cold water of ion-exchanger discharge with pH meter and conductivitimeter, after 1 year as a result, the pH of ion-exchanger water outlet is 8.52, and specific conductivity is 0.27 μ S/cm.
Embodiment 3
Present embodiment is used for illustrating the treatment process of electric generator inner cooling water of the present invention.
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains, H type ion exchange resin that preparation example 1 obtains are that 2: 0.85: 0.15 mixed is even according to volume ratio, obtain hybrid resin.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.72: 0.13.
The hybrid resin of preparation is seated in and decides in the cold water ion-exchanger, and the loadings of hybrid resin is 120 liters, then makes de-mineralized water with 3m
3The flow velocity of/h is by this ion exchange resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and specific conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by this ion-exchanger, contact with the ion exchange resin in the ion-exchanger, the time of described contact is 24 minutes, the temperature of contact is 45 ℃, thereby electric generator inner cooling water is handled, electric generator inner cooling water cycle after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, measure the pH value and the specific conductivity of the treated inner cold water of ion-exchanger discharge with pH meter and conductivitimeter, after 1 year as a result, the pH of ion-exchanger water outlet is 7.7-7.9, and specific conductivity is 0.12 μ S/cm.
Embodiment 4
Present embodiment is used for illustrating the treatment process of electric generator inner cooling water of the present invention.
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains, H type ion exchange resin that preparation example 1 obtains are that 2: 0.15: 0.85 mixed is even according to volume ratio, obtain hybrid resin.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.13: 0.72.
The hybrid resin of preparation is seated in and decides in the cold water ion-exchanger, and the loadings of hybrid resin is 120 liters, then makes de-mineralized water with 3m
3The flow velocity of/h is by this ion exchange resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and specific conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by this ion-exchanger, contact with the ion exchange resin in the ion-exchanger, the time of described contact is 24 minutes, the temperature of contact is 45 ℃, thereby electric generator inner cooling water is handled, electric generator inner cooling water cycle after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, measure the pH value and the specific conductivity of the treated inner cold water of ion-exchanger discharge with pH meter and conductivitimeter, after 4 months as a result, the pH of ion-exchanger water outlet is 7.5, specific conductivity is 0.13 μ S/cm, and the pH value of ion-exchanger water outlet after 5 months is reduced to and is lower than 7.0.
Embodiment 5
Present embodiment is used for illustrating the treatment process of electric generator inner cooling water of the present invention.
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains, H type ion exchange resin that preparation example 1 obtains are that 2: 0.9: 0.1 mixed is even according to volume ratio, obtain hybrid resin.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.76: 0.084.
The hybrid resin of preparation is seated in and decides in the cold water ion-exchanger, and the loadings of hybrid resin is 120 liters, then makes de-mineralized water with 3m
3The flow velocity of/h is by this ion exchange resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and specific conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by this ion-exchanger, contact with the ion exchange resin in the ion-exchanger, the time of described contact is 24 minutes, the temperature of contact is 45 ℃, thereby electric generator inner cooling water is handled, electric generator inner cooling water cycle after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, measure the pH value and the specific conductivity of the treated inner cold water of ion-exchanger discharge with pH meter and conductivitimeter, after 4 months as a result, the pH of ion-exchanger water outlet fluctuates between 7.8-8.1, specific conductivity is 0.36 μ S/cm, and ion-exchanger goes out electrical conductivity of water and progressively increases to being higher than 1.5 μ S/cm after 5 months.
Comparative Examples 1
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains are to mix at 2: 1 according to volume ratio, obtain hybrid resin.In this hybrid resin, the mol ratio of the ion-exchange group in ion-exchange group in the OH type ion exchange resin and the Na type ion exchange resin is 1: 0.84.
The hybrid resin of preparation is seated in and decides in the cold water ion-exchanger, and the loadings of hybrid resin is 120 liters, then makes de-mineralized water with 3m
3The flow velocity of/h is by this ion exchange resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and specific conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by this ion-exchanger, contact with the ion exchange resin in the ion-exchanger, the time of described contact is 24 minutes, the temperature of contact is 45 ℃, thereby electric generator inner cooling water is handled, electric generator inner cooling water cycle after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, measure the pH value and the specific conductivity of the treated inner cold water of ion-exchanger discharge with pH meter and conductivitimeter, after 3 months as a result, the pH of ion-exchanger water outlet is 8.5, specific conductivity is 1.4 μ S/cm, and ion-exchanger goes out electrical conductivity of water and continues to be increased to and be higher than 2.0 μ S/cm after 4 months.
Comparative Examples 2
The Na type ion exchange resin that the OH type ion exchange resin that obtains of preparation Comparative Examples 3, preparation Comparative Examples 2 are obtained, the H type ion exchange resin that preparation Comparative Examples 1 obtains are that 2: 0.64: 0.16 mixed is even according to volume ratio, obtain hybrid resin.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.68: 0.17.
The hybrid resin of preparation is seated in and decides in the cold water ion-exchanger, and the loadings of hybrid resin is 120 liters, then makes de-mineralized water with 3m
3The flow velocity of/h is by this ion exchange resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and specific conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by this ion-exchanger, contact with the ion exchange resin in the ion-exchanger, the time of described contact is 24 minutes, the temperature of contact is 45 ℃, thereby electric generator inner cooling water is handled, electric generator inner cooling water cycle after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, measure the pH value and the specific conductivity of the treated inner cold water of ion-exchanger discharge with pH meter and conductivitimeter, after 3 months as a result, the pH of ion-exchanger water outlet is 8.0, and specific conductivity is 1.6 μ S/cm.
Table 2 has been listed the composition and the test result of embodiment 1-5 and Comparative Examples 1 and 2 hybrid resins that use.
Table 2
*: the test data after 5 months;
*: the test data after 4 months.
Embodiment 1-5 and Comparative Examples 1 are compared as can be seen, if ion exchange resin does not contain H type ion exchange resin, and only contain OH type ion exchange resin and Na type ion exchange resin, although can significantly improve the pH value of electric generator inner cooling water, the specific conductivity of electric generator inner cooling water can not be remained for a long time below the 1.5 μ S/cm.
With embodiment 2 and 3 and Comparative Examples 2 compare as can be seen, under the essentially identical condition of other condition, OH type ion exchange resin in the hybrid resin, Na type ion exchange resin and H type ion exchange resin all adopt the gel-type styrene ion exchange resin to demonstrate the pH value of better stable generator inner cold water and the performance of specific conductivity, not only can be for a long time the pH value of electric generator inner cooling water be remained more than 7.5, but also can be for a long time the specific conductivity of electric generator inner cooling water be remained below the 0.3 μ S/cm.Yet, when the OH type ion exchange resin in the hybrid resin, Na type ion exchange resin and H type ion exchange resin are macroreticular ion exchange resin, can not be for a long time the specific conductivity of electric generator inner cooling water be remained below the 1.5 μ S/cm.
Claims (12)
1. the treatment process of an electric generator inner cooling water, this method comprises electric generator inner cooling water is contacted with ion exchange resin, it is characterized in that, described ion exchange resin is the hybrid resin that contains OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and described OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin gel-type ion-exchange resin of respectively doing for oneself.
2. method according to claim 1, wherein, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is 1: 0.1-0.8: 0.08-0.75.
3. method according to claim 2, wherein, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is 1: 0.4-0.75: 0.1-0.45.
4. method according to claim 3, wherein, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is 1: 0.65-0.75: 0.1-0.2.
5. method according to claim 1, wherein, described gel-type ion-exchange resin is the polystyrene gel-type ion-exchange resin.
6. according to any described method among the claim 2-4, wherein, the operating capacity of described OH type ion exchange resin be the 450-600 mmole/liter, the operating capacity of the operating capacity of described Na type ion exchange resin and H type ion exchange resin respectively do for oneself the 950-1010 mmole/liter.
7. according to any described method among the claim 1-4, wherein, the ion-exchange group of described OH type ion exchange resin is-N (CH
3)
3OH, the ion-exchange group of described Na type ion exchange resin is-SO
3Na, the ion-exchange group of described H type ion exchange resin is-SO
3The H group.
8. method according to claim 1, wherein, the condition of described contact makes that the pH value of the electric generator inner cooling water after contacting is 7-10, specific conductivity is 0.1-2 μ S/cm.
9. method according to claim 8, wherein, the condition of described contact makes that the pH value of the electric generator inner cooling water after contacting is 7.5-9, specific conductivity is 0.1-1.5 μ S/cm.
10. method according to claim 8, wherein, the time of described contact is 0.1-2 hour, the temperature of described contact is 20-80 ℃.
11. method according to claim 10, wherein, the time of described contact is 0.1-1 hour, and the temperature of described contact is 40-60 ℃.
12. method according to claim 1, wherein, the pH value of the electric generator inner cooling water before the contact is 5.5-6.5, and specific conductivity is 0.1-3 μ S/cm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092817A (en) * | 2011-01-06 | 2011-06-15 | 浙江大学 | Method for preparing ion exchange resin used for processing internal cold water of generator stator |
| CN110902761A (en) * | 2019-11-28 | 2020-03-24 | 武汉大学 | Method for adjusting pH value and conductivity of laboratory desalted water |
| CN110927052A (en) * | 2019-11-28 | 2020-03-27 | 武汉大学 | Dynamic coupon test method for red copper |
| CN112573615A (en) * | 2019-09-29 | 2021-03-30 | 西安正清和环境科技有限公司 | Development process of nuclear-grade internal cooling water resin |
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| CN101274789A (en) * | 2007-12-27 | 2008-10-01 | 武汉大学 | Ion exchange resin, use and use method thereof |
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| CN101274789A (en) * | 2007-12-27 | 2008-10-01 | 武汉大学 | Ion exchange resin, use and use method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102092817A (en) * | 2011-01-06 | 2011-06-15 | 浙江大学 | Method for preparing ion exchange resin used for processing internal cold water of generator stator |
| CN112573615A (en) * | 2019-09-29 | 2021-03-30 | 西安正清和环境科技有限公司 | Development process of nuclear-grade internal cooling water resin |
| CN110902761A (en) * | 2019-11-28 | 2020-03-24 | 武汉大学 | Method for adjusting pH value and conductivity of laboratory desalted water |
| CN110927052A (en) * | 2019-11-28 | 2020-03-27 | 武汉大学 | Dynamic coupon test method for red copper |
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