CN105417668B - A kind of compound basifier and application thereof - Google Patents
A kind of compound basifier and application thereof Download PDFInfo
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- CN105417668B CN105417668B CN201510999763.6A CN201510999763A CN105417668B CN 105417668 B CN105417668 B CN 105417668B CN 201510999763 A CN201510999763 A CN 201510999763A CN 105417668 B CN105417668 B CN 105417668B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Basifier is combined the invention discloses a kind of nuclear power station secondary loop, it is formulated by bi-component or multicomponent volatile alkaline substance, at least it is more than one kind that vapour-liquid distribution factor at 1 alkaline A classes material a kind of and 150 300 DEG C is less than 1 alkaline B classes material, and compound basifier satisfaction containing vapour-liquid distribution factor at 150 300 DEG C in the component of the compound basifier：When the distribution of first time vapour-liquid occurring under the conditions of at 150 300 DEG C, the ratio K of vapour phase alkali total mol concentration and liquid phase alkali total mol concentration is 1.0~1.5, when second of vapour-liquid distribution occurring under the conditions of at 150 300 DEG C, the ratio K of vapour phase alkali total mol concentration and liquid phase alkali total mol concentration is 0.5~1.0.The present invention can avoid or reduce the environmental pollution brought using single inorganic ammonia or organic amine, aggravate that mixed bed operation burden, operating cost is high, the problems such as the iron ion content in the too low condensates brought of pH is higher.
Description
Technical field
The invention belongs to nuclear power station water chemistry field, and in particular to a kind of compound basifier and application thereof.
Background technology
In the in-service nuclear power generating sets of current China, the secondary circuit of most nuclear power generating sets is using full volatilization (AVT) water chemistry
Treatment technology, i.e., by adding ammonia (NH3) and diamine (N2H4) to control the pH value and oxygen content of secondary coolant circuit system respectively.But
The vapour-liquid distribution factor of ammonia is higher, and most of ammonia are present in vapour phase during high temperature, and ammonia content is seriously relatively low in liquid phase so that nuclear power
Stand secondary circuit separator system, high-pressure heater system, oxygen-eliminating device system, low-pressure heater system, steam conversion
Device system, feed-water heater drained water recovery system, turbine driven feedwater pump system, main feed pump steam turbine drained water recovery system, feedwater
The position such as flow control system, steam-turbine and draining system pH value is relatively low, easily causes these positions to occur flowing and accelerates
Corrode (FAC).Occur once to cause mass casualties and huge in the FAC accidents of Japanese Mihama NPP and Sa Li nuclear power plants of the U.S.
Volume property loss.Not long ago, find that the hydrophobic 90 degree of joints of collector of secondary circuit are leaked during domestic certain nuclear power generating sets operation,
Subsequent overhaul carries out thickness measuring inspection to the collector, as a result finds that the hydrophobic collector wall thickness is substantially thinned, thinnest part is only 3mm,
And the former specification of the collector pipeline section is
The FAC problems brought for AVT water chemistry technologies, MIT proposes high ph-values and volatilized full water process
Technology (High-AVT), three nuclear powers of China designed by MIT and Haiyang nuclear power (AP1000 units), which are intended selecting, to be somebody's turn to do
Technical scheme.The essence of the technical scheme is：On the premise of basifier species and its vapour-liquid distribution character is not changed, two are improved
The total content of ammonia in the feedwater of loop, so as to improve the absolute dense of ammonia in the positions such as secondary circuit draining system, vehicle repair major streaming system
Degree and pH value, reaching prevents FAC purpose.But it is reported that the technical scheme is not suitable for the secondary circuit system for having cupric equipment
System, and the secondary circuit condensate polishing treatment mixed bed cycle of operation, increase mixed bed regeneration times and soda acid consumption, increase can be greatly shortened
Operations staff's work load.
To prevent FAC problems, the U.S., France are then proposed substitutes ammonia as two using organic amine (such as monoethanolamine, morpholine)
The technical scheme of loop basifier, the CAP1400 of China's independent research intends using monoethanolamine water chemistry control technology.The technical side
The essence of case is：The vapour-liquid distribution factor of organic amine is relatively low, and most of organic amines are present in liquid phase during high temperature, so as to have
Effect improves the absolute concentration and pH value of organic amine in secondary circuit draining system, vehicle repair major streaming system, and reaches and prevent FAC mesh
's.Domestic and international nuclear power station the actual running results show：Organic amine water chemistry technology can effectively slow down secondary circuit draining system and vapour
The flowing accelerated corrosion at the positions such as liquid two-phase system, lowers the iron ion in draining system (such as separator is hydrophobic)
Concentration, and then reduce the deposition of migration and its oxide of the iron ion into steam generator.However, single organic amine water chemistry
Technology still suffers from following drawback：
1) the identical pH value that feeds water is maintained, the addition (mass concentration) of organic amine must significantly be higher than ammonia, and monoethanolamine
Price be ammonia seven to ten times (morpholine be 2.3 dollars/kilogram, monoethanolamine be 1.5 dollars/kilogram, concentrated ammonia liquor is about 0.2
Dollar/kilogram), therefore nuclear power plant's operating cost is higher.As it can be seen from table 1 one phase of Qinshan secondary circuit water-chemical regime by ammonia+
Diamine (AVT) switchs to after monoethanolamine (ETA)+diamine, the water chemistry operating cost of secondary circuit still on floated 24%；
Monthly operating cost contrast (ten thousand yuan) before and after the conversion of table one phase of 1 Qinshan secondary circuit water-chemical regime
2) organic amine (such as monoethanolamine) can be inevitably generated thermal decomposition product (organic acid), not only result in condensate fine
The hydrogen conductivity rise of processing system and steam generator blowdown system, disturbs On-line monitor and the steam generation of Steam Condenser Leak
The blowdown of device；And organic acid presence can also cause the regeneration efficiency of precision processing mixed bed to drop to ethanol from the 100% of AMMONIA TREATMENT
The 80% of amine processing, therefore need when steam generator blowdown desalination and precision processing device of condensation water are designed to consider this influence.
3) because the vapour-liquid distribution coefficient of organic amine (such as monoethanolamine) is relatively low, the overwhelming majority is still deposited among liquid phase, this
The operation burden of steam generator (SG) drainage resin bed will certainly be aggravated；It also can result in secondary coolant circuit system local ph
Relatively low (such as condensate system), and then make it that iron ion content is higher in condensate；
4) using single organic amine also exist pollution environment in terms of the problem of, it was reported that using organic amine nuclear power plant its
Nitrogen content is higher in COD and regeneration waste in the waste water of discharge, and some organic amines are not only more stable, also have
Certain biology toxicity, is difficult that it is separated and removed by common Waste Water Treatment, considerably increases three-protection design
Cost.
The content of the invention
The technology drawback that the present invention is existed using single inorganic ammonia or organic amine for active service nuclear power station secondary loop there is provided
A kind of compound basifier, the compound basifier rationally coordinates two kinds or more of vapour-liquid distribution factors are different, thus avoid or
Reduce it is using single inorganic ammonia or organic amine and bring environmental pollution, aggravate that mixed bed operation burden, operating cost is high, pH mistakes
The problems such as iron ion content in the condensate that low strap comes is higher.
To solve above-mentioned technical problem, the present invention uses following technical scheme：
A kind of compound basifier, compound basifier is formulated by bi-component or multicomponent volatile alkaline substance, and extremely
When containing a kind of 150-300 DEG C less vapour-liquid distribution factor be more than 1 alkaline A classes material and vapour-liquid is distributed at a kind of 150-300 DEG C
The factor is less than 1 alkaline B classes material, and compound basifier is met：The distribution of first time vapour-liquid occurs under the conditions of at 150-300 DEG C
When, the ratio K of vapour phase alkali total mol concentration and liquid phase alkali total mol concentration be at 1.0~1.5,150-300 DEG C under the conditions of occur
During second of vapour-liquid distribution, the ratio K of vapour phase alkali total mol concentration and liquid phase alkali total mol concentration is 0.5~1.0,
,
Wherein：Refer to the molar concentration μm ol/L of A, B, component C in vapour phase in compound basifier,
AndRefer to the molar concentration μm ol/L of A, B, component C in the liquid phase in compound basifier.
Alkaline A classes material can for ammonia, 3- METHOXY PROPYL AMINEs (MPA), dimethylamine (DMA), pyrrolidines (PYRR) or
Quinoline (MPH).
Alkaline B classes material mainly includes：2- amino-2-methyl hydroxymalonic acid amine (AMP), monoethanolamine (ETA), 5- amino penta
Alcohol (5AP) or 4- amino butanols (4AB).
When the distribution of first time vapour-liquid occurring under the conditions of at 150-300 DEG C, vapour phase alkali total mol concentration and liquid phase alkali total moles
The ratio K of concentration is 1.2.
This can cause more basifiers to be assigned in main steam, and bring following benefit：Ensureing steam generator
While sewer pH, the total consumption of basifier is reduced；Reduce steam generator blowdown water mixed bed burden；For secondary circuit follow-up system
The pH controls of (such as draining system, condensate system) provide enough basifiers.
When second of vapour-liquid distribution occurring under the conditions of at 150-300 DEG C, vapour phase alkali total mol concentration and liquid phase alkali total moles
The ratio K of concentration is 0.8.
This can cause more basifiers be assigned to it is hydrophobic in, and bring following benefit：In the same of guarantee condensate pH
When, reduction condensate polishing treatment mixed bed burden；The pH value of draining system is improved, the corrosion control of draining system is more beneficial for；Drop
The total content of corrosion product in low feedwater.
Application of the foregoing compound basifier in regulation nuclear power station secondary loop main system pH value.
The pH value for adjusting each position of nuclear power station secondary loop main system is 9.30~10.00 at 25 DEG C.Compound basifier should
Used time, the position of each in secondary coolant circuit system need to be controlled to be combined the concentration of each component in basifier, and monitor feedwater piping in real time
Feedwater, steam generator blowdown water, main steam line main steam, condenser condensed water and draining system it is hydrophobic in compound alkalization
The concentration of the component of each in agent, it is ensured that compound basifier is when occurring vapour-liquid distribution, and vapour phase alkali total mol concentration and liquid phase alkali are total
The ratio K of molar concentration is located in predetermined scope.
Compared with prior art, the beneficial effects of the invention are as follows：
1) compound basifier of the invention can more effectively control each position of nuclear power station secondary loop system to be in higher pH
Value, effectively prevents each draining system of nuclear power station secondary loop and steam-hydrophobic two-phase flow system from FAC occur；
2) further to reduce the metal ion such as iron ion in nuclear power station secondary loop feedwater total for compound basifier of the invention
Concentration, reduce migration from corrosion product to steam generator secondary side, deposition；
3) compound basifier of the invention can reduce steam generator blowdown system simultaneously and condensed water precision processing system is mixed
The operation burden of bed, reduces the overall regeneration times, overall acid and alkali consumption amount and total water consumption of mixed-bed resin, mitigates operations staff
Work load；
4) compound basifier of the invention can reduce adverse effect of the basifier catabolite to nuclear power secondary coolant circuit system, especially
It is the hydrogen conductivity influence on condenser leakage monitoring and steam generator blowdown monitoring；
5) compound basifier of the invention can reduce nuclear power station secondary loop operation for individually organic amine is used
Expense；
6) compound basifier of the invention for individually organic amine is used, can reduce the waste liquid row of organic matter
Put, reduce the pollution to environment.
Embodiment
The present invention is further illustrated below.Embodiments of the present invention include but is not limited to the following example.
Embodiment 1
Compound alkalizing agent component composition：Monoethanolamine (ETA), ammonia (NH3)
Compound basifier initial mass concentration proportioning：[ETA]/[NH3]=2:1；
Table 2, which is combined basifier, is used for the monitor value of nuclear power station secondary loop
Example 2
Compound alkalizing agent component composition：5- aminopentanols (5-AP), dimethylamine (DMA)
Compound basifier initial mass concentration proportioning：[5-AP]/[DMA]=1:1；
Table 3, which is combined basifier, is used for the monitor value of nuclear power station secondary loop
Example 3
Compound alkalizing agent component composition：Monoethanolamine (ETA), ammonia (NH3), morpholine (MPH)
Compound basifier initial mass concentration proportioning：[ETA]/[NH3]/[MPH]=1:1:2；
Table 4, which is combined basifier, is used for the monitor value of nuclear power station secondary loop
It is embodiments of the invention as described above.The present invention is not limited to the above-described embodiments, anyone should learn that
The structure change made under the enlightenment of the present invention, the technical schemes that are same or similar to the present invention each fall within this
Within the protection domain of invention.
Claims (7)
1. a kind of compound basifier, it is characterised in that：Compound basifier is prepared by bi-component or multicomponent volatile alkaline substance
Vapour-liquid distribution factor is more than 1 alkaline A classes material and at a kind of 150-300 DEG C when forming, and at least containing a kind of 150-300 DEG C
Vapour-liquid distribution factor is less than 1 alkaline B classes material, and compound basifier is met：Occur for the first time under the conditions of at 150-300 DEG C
When vapour-liquid is distributed, the ratio K of vapour phase alkali total mol concentration and liquid phase alkali total mol concentration is bar at 1.0~1.5,150-300 DEG C
When second of vapour-liquid distribution occurring under part, the ratio K of vapour phase alkali total mol concentration and liquid phase alkali total mol concentration is 0.5~1.0,
,
Wherein：Refer to the molar concentration μm ol/L of A, B, component C in vapour phase in compound basifier, andRefer to the molar concentration μm ol/L of A, B, component C in the liquid phase in compound basifier.
2. compound basifier according to claim 1, it is characterised in that：Alkaline A classes material is ammonia, 3- methoxy-propyls
Amine, dimethylamine, pyrrolidines or morpholine.
3. compound basifier according to claim 1, it is characterised in that：Alkaline B classes material is：2- amino-2-methyls third
The acid amide of alcohol two, monoethanolamine, 5- aminopentanols or 4- amino butanols.
4. compound basifier according to claim 1, it is characterised in that：First time vapour occurs under the conditions of at 150-300 DEG C
When liquid is distributed, the ratio K of vapour phase alkali total mol concentration and liquid phase alkali total mol concentration is 1.2.
5. compound basifier according to claim 1, it is characterised in that：Second of vapour occurs under the conditions of at 150-300 DEG C
When liquid is distributed, the ratio K of vapour phase alkali total mol concentration and liquid phase alkali total mol concentration is 0.8.
6. the compound basifier as described in claim any one of 1-5 is adjusting the pH value at each position of nuclear power station secondary loop main system
On application.
7. application according to claim 6, it is characterised in that：The pH value at each position of regulation nuclear power station secondary loop main system exists
It is 9.30~10.00 at 25 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510999763.6A CN105417668B (en) | 2015-12-25 | 2015-12-25 | A kind of compound basifier and application thereof |
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| CN201510999763.6A CN105417668B (en) | 2015-12-25 | 2015-12-25 | A kind of compound basifier and application thereof |
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| CN105417668A CN105417668A (en) | 2016-03-23 |
| CN105417668B true CN105417668B (en) | 2017-10-13 |
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| CN111362388A (en) * | 2018-12-25 | 2020-07-03 | 中核核电运行管理有限公司 | Synergistic control method for ethanolamine and ammonia in two-loop thermodynamic system of nuclear power plant |
| CN109827998A (en) * | 2019-03-12 | 2019-05-31 | 广东核电合营有限公司 | Measure the concentration of basifier and the method for pH value relationship |
| CN110436599A (en) * | 2019-07-09 | 2019-11-12 | 中国船舶重工集团公司第七一九研究所 | A kind of regulator for marine small-sized heap |
| CN113603200A (en) * | 2021-08-20 | 2021-11-05 | 山东上远环保科技有限公司 | Boiler water feed water ph regulator |
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| RU2196114C2 (en) * | 1999-03-02 | 2003-01-10 | Научно-производственная фирма "Инкорсервис" | Hydrogen sulfide neutralizer in water-crude oil emulsions |
| JP4983069B2 (en) * | 2006-03-31 | 2012-07-25 | 栗田工業株式会社 | Pure water supply boiler water system treatment method and treatment apparatus |
| CN102557225A (en) * | 2010-12-28 | 2012-07-11 | 秦山核电有限公司 | Method for adjusting pH value of secondary circuit of nuclear power plant |
| CN102491480A (en) * | 2011-12-08 | 2012-06-13 | 上海德内克水处理设备有限公司 | Preparation method of steam recycling protecting agent |
| CN103307902B (en) * | 2013-05-22 | 2015-04-08 | 西安热工研究院有限公司 | Method for inhibiting corrosion to direct air-cooled condenser of power plant during operation |
| CN104593780B (en) * | 2014-12-22 | 2017-09-12 | 蔡杰 | A kind of steam circulation system conditioning agent and preparation method thereof |
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