CN101898813A - Method of cold water treatment in generator - Google Patents
Method of cold water treatment in generator Download PDFInfo
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- CN101898813A CN101898813A CN 201010238547 CN201010238547A CN101898813A CN 101898813 A CN101898813 A CN 101898813A CN 201010238547 CN201010238547 CN 201010238547 CN 201010238547 A CN201010238547 A CN 201010238547A CN 101898813 A CN101898813 A CN 101898813A
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- exchange resin
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- electric generator
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- 238000000034 method Methods 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 76
- 239000011347 resin Substances 0.000 claims abstract description 142
- 229920005989 resin Polymers 0.000 claims abstract description 142
- 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 48
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 34
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 34
- 239000000498 cooling water Substances 0.000 claims description 86
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 34
- 238000005341 cation exchange Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract description 48
- 239000003729 cation exchange resin Substances 0.000 abstract description 14
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000003957 anion exchange resin Substances 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 description 44
- 239000011734 sodium Substances 0.000 description 42
- 238000002360 preparation method Methods 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000003637 basic solution Substances 0.000 description 33
- 239000003929 acidic solution Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 238000005352 clarification Methods 0.000 description 12
- 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 12
- 239000000047 product Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 230000007935 neutral effect Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 230000004913 activation Effects 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 8
- 150000003440 styrenes Chemical class 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 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 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
A method for processing cold water in a generator comprises a step of contacting cold water in the generator with ion exchange resin, wherein the ion exchange resin is a mixed resin containing an OH type anion exchange resin, a Na type cation exchange resin and an H type cation exchange resin. By adopting the mixed resin provided by the invention to process the cold water in the generator, pH value of the cold water in the generator can be maintained to be above 7 steadily in a long term, and the conductivity of the cold water therein is maintained below 0.5mu S/cm, thus avoiding a stator cooling system of the generator from being corroded by the cold water in the generator.
Description
Technical field
The present invention relates to a kind of treatment process of electric generator inner cooling water.
Background technology
The stator of generator or rotor winding can produce a lot of heats in operation process, therefore, need cool off stator and rotor winding etc., and be aging with the winding that prevents to insulate.Generally, adopt the pure water (as condensed water or de-mineralized water) of low conductivity the generator unit stator cooling system to be implemented cooling as electric generator inner cooling water.Yet, electric generator inner cooling water is in the process of recycle, airborne oxygen and carbonic acid gas can dissolve in the electric generator inner cooling water, the pH value of electric generator inner cooling water is reduced, thereby cause the corrosion of generator unit stator cooling system hollow core copper conductor easily, the specific conductivity of electric generator inner cooling water is risen, influence generator insulating property over the ground, corrosion product also takes place easily (as cupric oxide, magnesium oxide, calcium oxide, sodium oxide, ferric oxide and phosphoric acid salt etc.) deposition, influence the cooling heat dissipation performance of generator windings line rod, even influence generator safety, operation economically.In order to eliminate the harm of electric generator inner cooling water poor water quality, electric generator inner cooling water adopts sodium type Zeo-karb to carry out purifying treatment usually.Yet sodium type Zeo-karb can only be at short notice maintains the pH value and the specific conductivity of electric generator inner cooling water in the scope that meets the demands, and can not control the water quality of electric generator inner cooling water steadily in the long term.
Summary of the invention
The present invention provides a kind of electric generator inner cooling water treatment method that can control the water quality of electric generator inner cooling water steadily in the long term for the treatment process that overcomes existing electric generator inner cooling water is difficult to the pH value of electric generator inner cooling water and specific conductivity are maintained defective in the scope that meets the demands steadily in the long term.
The invention provides a kind of treatment process of electric generator inner cooling water, this method comprises makes electric generator inner cooling water contact with ion exchange resin, wherein, described ion exchange resin is the hybrid resin that contains OH type anionite-exchange resin, Na type Zeo-karb and H type Zeo-karb.
According to the treatment process of electric generator inner cooling water provided by the invention, (use R by making electric generator inner cooling water and containing H type Zeo-karb
1H represents), Na type Zeo-karb (uses R
2Na represents) and OH type anionite-exchange resin (use R
3OH represents) hybrid resin contact, following reaction can take place with the ion in the electric generator inner cooling water in described H type Zeo-karb, Na type Zeo-karb and OH type anionite-exchange resin:
nR
1H+A
n+＝nR
1A+nH
+
nR
2Na+A
n+＝nR
2A+nNa
+
kR
3OH+B
k-＝kR
3B+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, not only can make the pH value of electric generator inner cooling water remain more than 7 for a long time, but also can the specific conductivity of electric generator inner cooling water not had a negative impact, specific conductivity is remained below the 0.5 μ S/cm for a long time, also can not cause corrosion simultaneously the generator unit stator cooling system.
Embodiment
The treatment process of electric generator inner cooling water according to the present invention comprises makes electric generator inner cooling water contact with ion exchange resin, wherein, described ion exchange resin is the hybrid resin that contains OH type anionite-exchange resin, Na type Zeo-karb and H type Zeo-karb.
According to method provided by the invention, as long as the pH value that the condition that electric generator inner cooling water contacts with ion exchange resin can make the electric generator inner cooling water after the contact for greater than 7 and less than 9, be preferably 7.2-8.5, specific conductivity is 0.1-2 μ S/cm, be 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 can be decided with the temperature of the inner electric generator inner cooling water of exporting of generator, and promptly the electric generator inner cooling 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 ℃.
According to method provided by the invention, the method that described electric generator inner cooling water is contacted with described hybrid resin can comprise makes the resin bed of described electric generator inner cooling water by being formed by described hybrid resin.In the preferred case, with respect to every cubic metre described hybrid resin, described electric generator inner cooling water is 10-50m by the flow of described hybrid resin
3/ h, more preferably 20-35m
3/ h.
In described hybrid resin, described OH type anionite-exchange resin, the mol ratio of the cation exchange groups in Na type Zeo-karb and the H type Zeo-karb can in very large range change, yet, be controlled to be more than 7.2 for the ease of pH value inner cold water, simultaneously electric conductivity of inside cold water is maintained below the 0.5 μ S/cm, thereby make water be fit to circulation as electric generator inner cooling water through obtaining after the described hybrid resin processing, and causticize electric generator inner cooling system (as the generator unit stator cooling system) not, described OH type anionite-exchange resin, the mol ratio of the cation exchange groups in Na type Zeo-karb and the H type Zeo-karb is preferably 1: 0.1-0.9: 0.1-0.9, more preferably 1: 0.2-0.45: 0.55-0.8.
Among the present invention, described ion-exchange group is meant when ion exchange resin contacts with electric generator inner cooling water, can carry out the group of ion-exchange with the ion in the electric generator inner cooling water, i.e. the effective ion cation exchange groups; The quantity of ion-exchange group is meant when ion exchange resin contacts with electric generator inner cooling water, can carry out the quantity of the ion-exchange group of ion-exchange with the ion in the electric generator inner cooling water, 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.
In the present invention, described operating capacity is meant the standard operation exchange capacity, and this standard operation exchange 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.
In the present invention, there is no particular limitation for the kind of described OH type anionite-exchange resin, Na type Zeo-karb and H type Zeo-karb, can suitably select in the ion exchange resin of routine separately.In preferred implementation of the present invention, described OH type anionite-exchange resin, Na type Zeo-karb and the H type Zeo-karb macroreticular ion exchange resin of respectively doing for oneself.In this case, abundant ion-exchange can take place with the mineral ion in the electric generator inner cooling water in hybrid resin according to the present invention, and can adsorb the macromolecule organic in the electric generator inner cooling water, thereby the pH value and the specific conductivity of electric generator inner cooling water can be controlled in the suitable scope.In the present invention, described macroreticular ion exchange resin is meant the resin that has the macroporous netlike three-dimensional arrangement and have cation exchange groups, the big internal surface that there is permanent duct in this resin inside and forms thus, and the surface-area of general every this resin of gram is 5m
2More than, be preferably 5-100m
2
In further preferred embodiment, described OH type anionite-exchange resin, Na type Zeo-karb and the H type Zeo-karb macroporous type styrene ion exchange resin of respectively doing for oneself.Described macroporous type styrene ion exchange resin can be for well known to a person skilled in the art various resins, for example, the molecular skeleton of described macroporous type styrene ion exchange resin can be styrene-divinylbenzene copolymer, and the degree of crosslinking of this multipolymer can be 4-8 mole %.In the present invention, described degree of crosslinking is meant the molecular fraction of divinylbenzene consumption in the styrene-divinylbenzene copolymer forming process.The coefficient of uniformity of described macroporous type styrene ion exchange resin can be 1.05-1.60, and rate of small round spheres can be for more than 90%.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.
In a kind of preferred embodiment, the cation exchange groups of described Na type Zeo-karb is-SO
3The Na group, and the operating capacity of described Na type Zeo-karb can for the 800-1200 mmole/liter, for example described Na type Zeo-karb can be Na type large hole strong acid styrene system cation exchange resin, described Na type large hole strong acid styrene system cation exchange resin can be commercially available, for example can be available from Zhengguang Resin Co., Ltd..
In the preferred embodiment of another kind, the cation exchange groups of described H type Zeo-karb is-SO
3The H group, the operating capacity of described H type Zeo-karb be the 800-1200 mmole/liter, for example described H type Zeo-karb can be H type large hole strong acid styrene system cation exchange resin, described Na type large hole strong acid styrene system cation exchange resin can be commercially available, for example can be available from Zhengguang Resin Co., Ltd..
In the preferred embodiment of another kind, the cation exchange groups of described OH type anionite-exchange resin is-N (CH
3)
3The OH group, the operating capacity of described OH type anionite-exchange resin be the 450-650 mmole/liter, for example described OH type anionite-exchange resin can be OH type macroporous strong basic styrene series anionite-exchange resin, described OH type macroporous strong basic styrene series anionite-exchange resin can be commercially available, for example can be available from Zhengguang Resin Co., Ltd..
According to method provided by the invention, when described OH type anionite-exchange resin, Na type Zeo-karb and H type Zeo-karb are respectively done for oneself macroreticular ion exchange resin when respectively doing for oneself macroreticular ion exchange resin, the water that described electric generator inner cooling water obtains after being preferably and adopting de-mineralized water as heat-eliminating medium generator to be cooled off.In this case, the pH value of described electric generator inner cooling water is 6.5 to less than 7, and specific conductivity is preferably 0.2 to less than 0.5 μ S/cm.In the present invention, described de-mineralized water is the finished product water that obtains after tap water is handled through anion exchanger, cation exchanger and mixed ion exchanger.
In the present invention, described hybrid resin can adopt conventional method preparation, for example OH type anionite-exchange resin, Na type Zeo-karb and H type Zeo-karb can be mixed.
In a kind of preferred implementation,, may further comprise the steps according to the preparation method of described hybrid resin provided by the invention for the hybrid resin that makes final preparation has more stable ion-exchange capacity:
(1) H type Zeo-karb is contacted with basic solution, contact with acidic solution again, obtain through activatory H type Zeo-karb;
(2) make contacting with the basic solution that contains sodium ion of obtaining in (1), obtain Na type Zeo-karb through activatory H type Zeo-karb;
(3) OH type anionite-exchange resin is contacted with acidic solution, contact with basic solution again, obtain through activatory OH type anionite-exchange resin;
(4) with obtain in (1) through mixing of obtaining in the Na type Zeo-karb that obtains in activatory H type Zeo-karb, (2) and (3) through activatory OH type anionite-exchange resin.
In above-mentioned steps (1), contact with basic solution by making H type Zeo-karb, contact with acidic solution again, so that H type Zeo-karb is activated, make that the H type Zeo-karb behind overactivation has stable ion-exchange capacity.In a kind of preferred implementation of the present invention, described H type Zeo-karb activatory method is comprised impregnated in the basic solution H type Zeo-karb, extremely neutral with the de-mineralized water washing again, make then to impregnated in the resin impregnation that obtains after the basic solution in acidic solution, and again with the de-mineralized water washing to neutral.Particularly, washing to the neutral process after H type Zeo-karb impregnated in basic solution can be washed to the transparent clarification of water quality and do not had phenolphthalein alkalinity and realize by the resin after will impregnated in basic solution with de-mineralized water; Washing after H type Zeo-karb impregnated in acidic solution can be washed by the resin after will impregnated in acidic solution with de-mineralized water to the transparent clarification of water quality, no methyl orange alkalinity and specific conductivity≤1.0 μ S/cm to the neutral process and to be realized.
There is no particular limitation for the condition that described H type Zeo-karb contacts with basic solution, can suitably select in the activation condition of the Zeo-karb of routine.Yet, can stably control the water quality of electric generator inner cooling water for the hybrid resin that makes final preparation, as improve the pH value of electric generator inner cooling water and reduce the specific conductivity of electric generator inner cooling water, the volume ratio of described H type Zeo-karb and basic solution is preferably 1: 1-10, more preferably 1: 1.5-5, more preferably 1: 1.8-3; The time that described H type Zeo-karb contacts with basic solution is preferably 1-20 hour, more preferably 5-12 hour.All there is no particular limitation for the kind of described basic solution and concentration, all can suitably select in the aqueous solution of the alkali of various routines, and for example described basic solution can be the NaOH solution of 1-15 weight % for concentration, is preferably the NaOH solution of 3-10 weight %.
The condition that the resin that H type Zeo-karb is obtained after contacting with basic solution contacts with acidic solution also can suitably selection in the activation condition of the Zeo-karb of routine.In the preferred case, the volume ratio of described H type Zeo-karb and described acidic solution is 1: 1-10, more preferably 1: 1.5-5, more preferably 1: the volume of the H type Zeo-karb before 1.8-3, the volume of described here H type Zeo-karb are meant and contact with described basic solution.Be preferably 1-20 hour, more preferably 5-12 hour with the time that resin after basic solution contacts contacts with described acidic solution.All there is no particular limitation for the kind of described acidic solution and concentration, and for example described acidic solution can be the HCl solution of 1-10 weight % for concentration, is preferably the HCl solution of 3-8 weight %.
In above-mentioned steps (2), described Na type Zeo-karb makes by the H type Zeo-karb after the activation is contacted with the basic solution that contains sodium ion, so the Na type Zeo-karb of preparation has more stable ion-exchange performance, thereby make the hybrid resin of final preparation can stably control the water quality of electric generator inner cooling water, as pH value that improves electric generator inner cooling water and the specific conductivity that reduces electric generator inner cooling water.In a kind of preferred implementation of the present invention, the preparation method of described Na type Zeo-karb comprises impregnated in the basic solution that contains sodium ion process activatory H type Zeo-karb, extremely neutral with the de-mineralized water washing again.Particularly, washing after H type Zeo-karb impregnated in the basic solution that contains sodium ion can be washed by the resin after will impregnated in this basic solution with de-mineralized water to the transparent clarification of water quality, no phenolphthalein alkalinity and specific conductivity≤1.0 μ S/cm to the neutral process and to be realized.
The condition that the H type Zeo-karb after the activation contacts with the basic solution that contains sodium ion in the step (1) can in very large range be changed.Yet, the H type Zeo-karb after the activation can fully be converted into Na type Zeo-karb in the step (1) in order to make, H type Zeo-karb in the step (1) after the activation is preferably 1 with the volume ratio that contains the basic solution of sodium ion: 1-10, more preferably 1: 1.5-5, more preferably 1: 1.8-3; The time that H type Zeo-karb in the step (1) after the activation contacts with the basic solution that contains sodium ion is preferably 10-50 hour, more preferably 20-30 hour.All there is no particular limitation for the kind of the described basic solution that contains sodium ion and concentration, can be the NaOH solution of 3-10 weight % for concentration for example, is preferably the NaOH solution of 4-8 weight %.
In above-mentioned steps (3), by OH type anionite-exchange resin is contacted with acidic solution, contact with basic solution again,, make that the OH type anionite-exchange resin behind overactivation has stable ion-exchange capacity so that OH type anionite-exchange resin is activated.In a kind of preferred implementation of the present invention, described OH type anionite-exchange resin activatory method is comprised impregnated in the acidic solution OH type anionite-exchange resin, extremely neutral with the de-mineralized water washing again, make then to impregnated in the resin impregnation that obtains after the acidic solution in basic solution, and again with the de-mineralized water washing to neutral.Particularly, washing to the neutral process after OH type anionite-exchange resin impregnated in acidic solution can be washed to the transparent clarification of water quality and do not had methyl orange alkalinity and realize by the resin after will impregnated in acidic solution with de-mineralized water; Washing after OH type anionite-exchange resin impregnated in basic solution can be washed by the resin after will impregnated in basic solution with de-mineralized water to the transparent clarification of water quality, no phenolphthalein alkalinity and specific conductivity≤1.0 μ S/cm to the neutral process and to be realized.
There is no particular limitation for the condition that described OH type anionite-exchange resin contacts with acidic solution, can suitably select in the activation condition of the anionite-exchange resin of routine.Yet, can stably control the water quality of electric generator inner cooling water for the hybrid resin that makes final preparation, as improve the pH value of electric generator inner cooling water and reduce the specific conductivity of electric generator inner cooling water, the volume ratio of described OH type anionite-exchange resin and acidic solution is preferably 1: 1-10, more preferably 1: 1.5-5, more preferably 1: 1.8-3; The time that described OH type anionite-exchange resin contacts with acidic solution is preferably 1-20 hour, more preferably 5-12 hour.All there is no particular limitation for the kind of described acidic solution and concentration, all can suitably select in the aqueous acid of various routines, and for example described acidic solution can be the HCl solution of 1-10 weight % for concentration, is preferably the HCl solution of 3-8 weight %.
The condition that the resin that OH type anionite-exchange resin is obtained after contacting with acidic solution contacts with basic solution also can suitably selection in the activation condition of the anionite-exchange resin of routine.In the preferred case, the volume ratio of described OH type anionite-exchange resin and described basic solution is 1: 1-10, more preferably 1: 1.5-5, more preferably 1: the volume of the OH type anionite-exchange resin before 1.8-3, the volume of described here OH type anionite-exchange resin are meant and contact with described acidic solution.Be preferably 1-20 hour, more preferably 5-12 hour with the time that resin after acidic solution contacts contacts with described basic solution.All there is no particular limitation for the kind of described basic solution and concentration, and for example described basic solution can be the NaOH solution of 1-15 weight % for concentration, is preferably the NaOH solution of 3-10 weight %.
According to described method provided by the invention, described step (1), (2) and (3) do not have strict working order, step (1), (2) and (3) are implemented successively, also can first implementation step (3) implementation step (1) and (2) again, even can also make step (1) and (3) implement again implementation step (2) simultaneously.
In above-mentioned steps (4), can adopt the method for various routines to implement through what obtain in the Na type Zeo-karb that obtains in activatory H type Zeo-karb, (2) and (3) through activatory OH type anionite-exchange resin blended method with what obtain in (1).
The invention will be further described by the following examples.
Embodiment 1
Present embodiment is used to illustrate the treatment process of electric generator inner cooling water provided by the invention.
＜preparation hybrid resin 〉
(1) with de-mineralized water with H type large hole strong acid styrene system cation exchange resin (available from Zhengguang Resin Co., Ltd., operating capacity is 950mmol/L, coefficient of uniformity is 1.09, rate of small round spheres is 90%) wash to the transparent clarification of water quality, make then this H type large hole strong acid styrene system cation exchange resin volume for 2 times of this resin, concentration is dipping 8 hours in the NaOH solution of 5 weight %, use de-mineralized water (pH value for 6.8-7.2, specific conductivity is less than 0.2 μ S/cm) to wash then and do not have phenolphthalein alkalinity to the transparent clarification of water quality; Make again this resin volume for 2 times of this resin, concentration is to soak 8 hours in the HCl solution of 5 weight %, (the pH value is 6.8-7.2 to use de-mineralized water afterwards, specific conductivity is less than 0.2 μ S/cm) wash to the transparent clarification of water quality, no methyl orange alkalinity and specific conductivity≤1.0 μ S/cm, thus obtain through activatory H type Zeo-karb.
(2) with in (1) through activatory H type Zeo-karb impregnated in volume for 2 times of this resin, concentration is dipping 24 hours in the NaOH solution of 5 weight %, wash to the transparent clarification of water quality, no phenolphthalein alkalinity and specific conductivity≤1.0 μ S/cm with de-mineralized water then, thereby obtain Na type Zeo-karb.
(3) with de-mineralized water with OH type macroporous strong basic styrene series anionite-exchange resin (available from Zhengguang Resin Co., Ltd., operating capacity is 450mmol/L, coefficient of uniformity is 1.09, rate of small round spheres is 90%) wash to the transparent clarification of water quality, make then this OH type macroporous strong basic styrene series anionite-exchange resin volume for 2 times of this resin, concentration is dipping 8 hours in the HCl solution of 5 weight %, wash to the transparent clarification of water quality with de-mineralized water then and do not have methyl orange alkalinity; Make again this resin volume for 2 times of this resin, concentration is to soak 8 hours in the NaOH solution of 5 weight %, wash to the transparent clarification of water quality, no phenolphthalein alkalinity and specific conductivity≤1.0 μ S/cm with de-mineralized water afterwards, thereby obtain through activatory OH type anionite-exchange resin.
(4) be 2: 0.3 with the H type Zeo-karb that makes in the Na type Zeo-karb that makes in the OH type anionite-exchange resin that makes in above-mentioned (3), (2) and (1) with volume ratio: thus 0.7 mix and obtain hybrid resin.
＜handle electric generator inner cooling water with hybrid resin 〉
To be filled in as the hybrid resin of above-mentioned preparation in the ion-exchange container, total amount of fill is 120L.Then, (the pH value is 6.8-7.2 with the de-mineralized water under the normal temperature, specific conductivity is less than 0.2 μ S/cm) injection generator unit stator cooling system enforcement cooling, and (the pH value is 6.5 to less than 7 to make the electric generator inner cooling water of discharging from the generator unit stator cooling system, specific conductivity is 0.3-0.4 μ S/cm) by the hybrid resin bed in the described ion-exchange container, make that be 24 minutes the duration of contact of described electric generator inner cooling water and described hybrid resin bed, the temperature of contact is 40-60 ℃.Then, will be circulated to through the electric generator inner cooling water after the described ion exchange resin treatment in the generator unit stator cooling system, thereby make described electric generator inner cooling water cycle implement cooling generator.
After making said process move 30 days continuously, measure the pH value and the specific conductivity of the water outlet of described ion-exchange container with pH meter and conductivitimeter, the pH value that records the water outlet of ion-exchange container is 8.5, specific conductivity is 0.25 μ S/cm, and, can see that by observing not forming corrosion product in the described generator unit stator cooling system precipitates.
Embodiment 2
Present embodiment is used to illustrate described hybrid resin provided by the invention and preparation method thereof.
＜preparation hybrid resin 〉
(1) method according to preparation example 1 prepares H type Zeo-karb, and different is that the H type large hole strong acid styrene system cation exchange resin's who is adopted operating capacity is 1200mmol/L.
(2) method according to preparation example 1 prepares Na type Zeo-karb, different is, that is adopted uses operating capacity to make (also being to make in (1) of preparation example 2) as the H type large hole strong acid styrene system cation exchange resin of 1200mmol/L through activatory H type Zeo-karb.
(3) method according to preparation example 1 prepares OH type anionite-exchange resin, and different is that the working capacity of the OH type macroporous strong basic styrene series anionite-exchange resin that is adopted is 600mmol/L.
(4) be 2: 0.2 with the H type Zeo-karb that makes in the Na type Zeo-karb that makes in the OH type anionite-exchange resin that makes in above-mentioned (3), (2) and (1) with volume ratio: thus 0.8 mix and obtain hybrid resin.
＜handle electric generator inner cooling water with hybrid resin 〉
To be filled in as the hybrid resin of above-mentioned preparation in the ion-exchange container, total amount of fill is 120L.Then, (the pH value is 6.8-7.2 with the de-mineralized water under the normal temperature, specific conductivity is less than 0.2 μ S/cm) injection generator unit stator cooling system enforcement cooling, and (the pH value is 6.5 to less than 7 to make the electric generator inner cooling water of discharging from the generator unit stator cooling system, specific conductivity is 0.3-0.4 μ S/cm) by the hybrid resin bed in the described ion-exchange container, make that be 30 minutes the duration of contact of described electric generator inner cooling water and described hybrid resin bed, the temperature of contact is 40-60 ℃.Then, will be circulated to through the electric generator inner cooling water after the described ion exchange resin treatment in the generator unit stator cooling system, thereby make described electric generator inner cooling water cycle implement cooling generator.
After making said process move 30 days continuously, measure the pH value and the specific conductivity of the water outlet of described ion-exchange container with pH meter and conductivitimeter, the pH value that records the water outlet of ion-exchange container is 7.8, specific conductivity is 0.28 μ S/cm, and, can see that by observing not forming corrosion product in the described generator unit stator cooling system precipitates.
Embodiment 3
Present embodiment is used to illustrate described hybrid resin provided by the invention and preparation method thereof.
＜preparation hybrid resin 〉
(1) method according to preparation example 1 prepares H type Zeo-karb, and different is that the H type large hole strong acid styrene system cation exchange resin's who is adopted operating capacity is 900mmol/L.
(2) method according to preparation example 1 prepares Na type Zeo-karb, different is, that is adopted uses operating capacity to make (also being to make in (1) of preparation example 3) as the H type large hole strong acid styrene system cation exchange resin of 900mmol/L through activatory H type Zeo-karb.
(3) method according to preparation example 1 prepares OH type anionite-exchange resin, and different is that the working capacity of the OH type macroporous strong basic styrene series anionite-exchange resin that is adopted is 450mmol/L.
(4) be 2: 0.4 with the H type Zeo-karb that makes in the Na type Zeo-karb that makes in the OH type anionite-exchange resin that makes in above-mentioned (3), (2) and (1) with volume ratio: thus 0.6 mix and obtain hybrid resin.
＜handle electric generator inner cooling water with hybrid resin 〉
To be filled in as the hybrid resin of above-mentioned preparation in the ion-exchange container, total amount of fill is 120L.Then, (the pH value is 6.8-7.2 with the de-mineralized water under the normal temperature, specific conductivity is less than 0.2 μ S/cm) injection generator unit stator cooling system enforcement cooling, and (the pH value is 6.5 to less than 7 to make the electric generator inner cooling water of discharging from the generator unit stator cooling system, specific conductivity is 0.3-0.4 μ S/cm) by the hybrid resin bed in the described ion-exchange container, make that be 20 minutes the duration of contact of described electric generator inner cooling water and described hybrid resin bed, the temperature of contact is 40-60 ℃.Then, will be circulated to through the electric generator inner cooling water after the described ion exchange resin treatment in the generator unit stator cooling system, thereby make described electric generator inner cooling water cycle implement cooling generator.
After making said process move 30 days continuously, measure the pH value and the specific conductivity of the water outlet of described ion-exchange container with pH meter and conductivitimeter, the pH value that records the water outlet of ion-exchange container is 8.2, specific conductivity is 0.29 μ S/cm, and, can see that by observing not forming corrosion product in the described generator unit stator cooling system precipitates.
Embodiment 4
Present embodiment is used to illustrate described hybrid resin provided by the invention and preparation method thereof.
＜preparation hybrid resin 〉
(1) method according to preparation example 1 prepares H type Zeo-karb, different is, with the H type gel-type strongly acidic styrene type cation exchange resin of equal volume (available from Rhom and Hass, model is UP6150, operating capacity is 1090mmol/L, coefficient of uniformity is 1.20, and rate of small round spheres is 96%) the described H type large hole strong acid styrene system cation exchange resin of replacement.
(2) method according to preparation example 1 prepares Na type Zeo-karb, and different is that to be adopted uses the H type Zeo-karb that makes in (1) of preparation example 4 through activatory H type Zeo-karb.
(3) method according to preparation example 1 prepares OH type anionite-exchange resin, different is, with the OH type gel type strong base styrene series anion exchange resin of equal volume (available from Dow Chemical, model is 550A, operating capacity is 600mmol/L, coefficient of uniformity is 1.09, and rate of small round spheres is 95%) the described OH type macroporous strong basic styrene series anionite-exchange resin of replacement.
(4) be 2: 0.3 with the H type Zeo-karb that makes in the Na type Zeo-karb that makes in the OH type anionite-exchange resin that makes in above-mentioned (3), (2) and (1) with volume ratio: thus 0.7 mix and obtain hybrid resin.
＜handle electric generator inner cooling water with hybrid resin 〉
To be filled in as the hybrid resin of above-mentioned preparation in the ion-exchange container, total amount of fill is 120L.Then, (the pH value is 6.8-7.2 with the de-mineralized water under the normal temperature, specific conductivity is less than 0.2 μ S/cm) injection generator unit stator cooling system enforcement cooling, and (the pH value is 6.5 to less than 7 to make the electric generator inner cooling water of discharging from the generator unit stator cooling system, specific conductivity is 0.3-0.4 μ S/cm) with the flow of 3m3/h by the hybrid resin bed in the described ion-exchange container, make that be 24 minutes the duration of contact of described electric generator inner cooling water and described hybrid resin bed, the temperature of contact is 40-60 ℃.Then, will be circulated to through the electric generator inner cooling water after the described ion exchange resin treatment in the generator unit stator cooling system, thereby make described electric generator inner cooling water cycle implement cooling generator.
After making said process move 30 days continuously, measure the pH value and the specific conductivity of the water outlet of described ion-exchange container with pH meter and conductivitimeter, the pH value that records the water outlet of ion-exchange container is 7.1, specific conductivity is 0.35 μ S/cm, and, can see that by observing being formed with a spot of corrosion product in the described generator unit stator cooling system precipitates.
By embodiment 1 and embodiment 4 are compared as can be seen, though the total exchange capacity and the operating capacity of the ion exchange resin that adopts among the embodiment 1 are less, the hybrid resin of the ion exchange resin of embodiment 1 can be adjusted to electric generator inner cooling water higher pH value and littler specific conductivity.
Embodiment 5
Present embodiment is used to illustrate the hybrid resin that is used to handle electric generator inner cooling water of the present invention.
Method according to embodiment 1 makes the electric generator inner cooling water cycle enter described ion-exchange container and generator unit stator cooling system, different is, described hybrid resin is OH type anionite-exchange resin, Na type Zeo-karb and the H type Zeo-karb that will make in the preparation example with volume ratio is to mix at 2: 0.15: 0.85 to make.After described generator unit stator cooling system and ion-exchange container move 30 days continuously, the pH value that records the water outlet of ion-exchange container is 7.2, specific conductivity is 0.32 μ S/cm, and, can see that by observing being formed with a spot of corrosion product in the described generator unit stator cooling system precipitates.
Embodiment 6
Present embodiment is used to illustrate the hybrid resin that is used to handle electric generator inner cooling water of the present invention.
Method according to embodiment 1 makes the de-mineralized water circulation enter described ion-exchange container and generator unit stator cooling system, different is, described hybrid resin is OH type anionite-exchange resin, Na type Zeo-karb and the H type Zeo-karb that will make in the preparation example with volume ratio is to mix at 2: 0.6: 0.4 to make.After described generator unit stator cooling system and ion-exchange container move 30 days continuously, the pH value that records the water outlet of ion-exchange container is 7.3, specific conductivity is 0.34 μ S/cm, and, can see that by observing being formed with a spot of corrosion product in the described generator unit stator cooling system precipitates.
Comparative Examples 1
Method according to embodiment 1 makes the de-mineralized water circulation enter described ion-exchange container and generator unit stator cooling system, different is, described hybrid resin is the OH type anionite-exchange resin that will make in the preparation example and Na type Zeo-karb with volume ratio is to mix at 2: 0.3 to make.After described generator unit stator cooling system and ion-exchange container move 30 days continuously, the pH value that records the water outlet of ion-exchange container is 6.8, specific conductivity is 2.08 μ S/cm, and, can see that by observing being formed with a large amount of corrosion products in the described generator unit stator cooling system precipitates.
Comparative Examples 2
Method according to embodiment 1 makes the de-mineralized water circulation enter described ion-exchange container and generator unit stator cooling system, different is, described hybrid resin is the Na type Zeo-karb that will make in the preparation example and H type Zeo-karb with volume ratio is to mix at 0.3: 0.7 to make.After described generator unit stator cooling system and ion-exchange container move 30 days continuously, the pH value that records the water outlet of ion-exchange container is 6.8, specific conductivity is 2.13 μ S/cm, and, can see that by observing being formed with a large amount of corrosion products in the described generator unit stator cooling system precipitates.
Comparative Examples 3
Method according to embodiment 1 makes the de-mineralized water circulation enter described ion-exchange container and generator unit stator cooling system, and different is to replace described hybrid resin with the Na type Zeo-karb that makes in 120 liters the preparation example.After described generator unit stator cooling system and ion-exchange container move 30 days continuously, the pH value that records the water outlet of ion-exchange container is 6.5, specific conductivity is 2.25 μ S/cm, and, can see that by observing being formed with a large amount of corrosion products in the described generator unit stator cooling system precipitates.
This shows, adopting described hybrid resin provided by the invention that electric generator inner cooling water is handled can be for a long time and the pH value of inner cold water is maintained more than 7, electric conductivity of inside cold water is maintained below the 0.5 μ S/cm, thereby make electric generator inner cooling water can not cause corrosion the generator unit stator cooling system.
Claims (12)
1. the treatment process of an electric generator inner cooling water, this method comprises makes electric generator inner cooling water contact with ion exchange resin, it is characterized in that described ion exchange resin is the hybrid resin that contains OH type anionite-exchange resin, Na type Zeo-karb and H type Zeo-karb.
2. method according to claim 1, wherein, in described hybrid resin, the mol ratio of the cation exchange groups in described OH type anionite-exchange resin, Na type Zeo-karb and the H type Zeo-karb is 1: 0.1-0.9: 0.1-0.9.
3. method according to claim 2, wherein, in described hybrid resin, the mol ratio of the cation exchange groups in described OH type anionite-exchange resin, Na type Zeo-karb and the H type Zeo-karb is 1: 0.2-0.45: 0.55-0.8.
4. according to any described method among the claim 1-3, wherein, described OH type anionite-exchange resin, Na type Zeo-karb and the H type Zeo-karb macroreticular ion exchange resin of respectively doing for oneself.
5. method according to claim 4, wherein, described OH type anionite-exchange resin, Na type Zeo-karb and the H type Zeo-karb macroporous type styrene ion exchange resin of respectively doing for oneself.
6. method according to claim 5, wherein, the cation exchange groups of described Na type Zeo-karb is-SO
3Na, the cation exchange groups of described H type Zeo-karb is-SO
3The H group, the cation exchange groups of described OH type anionite-exchange resin is-N (CH
3)
3The OH group.
7. according to any described method among the claim 1-3, wherein, the operating capacity of described Na type Zeo-karb be the 800-1200 mmole/liter, the operating capacity of described H type Zeo-karb be the 800-1200 mmole/liter, the operating capacity of described OH type anionite-exchange resin be the 450-650 mmole/liter.
8. method according to claim 1, wherein, the pH value of the electric generator inner cooling water after the feasible contact of the condition of described contact is greater than 7 and less than 9, and 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 7.2-8.5, specific conductivity is 0.1-0.5 μ S/cm.
10. according to claim 1,8 or 9 described methods, wherein, the time that described electric generator inner cooling water contacts with ion exchange resin is 0.1-2 hour, and the temperature of contact is 20-80 ℃.
11. method according to claim 10, wherein, the time that described electric generator inner cooling water contacts with ion exchange resin is 0.1-1 hour, and the temperature of contact is 40-60 ℃.
12. method according to claim 1, wherein, the pH value of described electric generator inner cooling water is 6.5 to less than 7, and specific conductivity is 0.2 to less than 0.5 μ S/cm.
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Cited By (7)
| 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 |
| CN102557190A (en) * | 2012-02-23 | 2012-07-11 | 宁波争光树脂有限公司 | Mixed-bed resin for polishing condensate of compatible supercritical unit |
| CN102557191A (en) * | 2012-02-23 | 2012-07-11 | 宁波争光树脂有限公司 | Process for synthesizing powdered ion-exchange resin |
| CN103803676A (en) * | 2013-12-30 | 2014-05-21 | 中国神华能源股份有限公司 | Method for removing arsenic in water |
| CN111943318A (en) * | 2020-08-28 | 2020-11-17 | 哈尔滨安泰利达科技开发有限公司 | Special resin for generator inner cooling water and preparation method thereof |
| CN113603188A (en) * | 2021-08-31 | 2021-11-05 | 深圳妈湾电力有限公司 | Resin treatment method for treatment of cold water in generator |
| CN115196718A (en) * | 2022-07-13 | 2022-10-18 | 北京师范大学 | Circulating cooling water treatment method |
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Cited By (8)
| 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 |
| CN102557190A (en) * | 2012-02-23 | 2012-07-11 | 宁波争光树脂有限公司 | Mixed-bed resin for polishing condensate of compatible supercritical unit |
| CN102557191A (en) * | 2012-02-23 | 2012-07-11 | 宁波争光树脂有限公司 | Process for synthesizing powdered ion-exchange resin |
| CN102557190B (en) * | 2012-02-23 | 2014-08-06 | 宁波争光树脂有限公司 | Mixed-bed resin for polishing condensate of compatible supercritical unit |
| CN103803676A (en) * | 2013-12-30 | 2014-05-21 | 中国神华能源股份有限公司 | Method for removing arsenic in water |
| CN111943318A (en) * | 2020-08-28 | 2020-11-17 | 哈尔滨安泰利达科技开发有限公司 | Special resin for generator inner cooling water and preparation method thereof |
| CN113603188A (en) * | 2021-08-31 | 2021-11-05 | 深圳妈湾电力有限公司 | Resin treatment method for treatment of cold water in generator |
| CN115196718A (en) * | 2022-07-13 | 2022-10-18 | 北京师范大学 | Circulating cooling water treatment method |
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