CN113248032A - Method for adjusting circulating water scale and corrosion inhibitor formula based on make-up water calcium-base ratio - Google Patents
Method for adjusting circulating water scale and corrosion inhibitor formula based on make-up water calcium-base ratio Download PDFInfo
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a method for adjusting a circulating water scale and corrosion inhibitor formula based on a make-up water calcium-base ratio, wherein the circulating water scale and corrosion inhibitor comprises an organic phosphine scale inhibitor A, aminotrimethylene phosphonic Acid (ATMP), a dispersion scale inhibitor B, maleic acid-acrylic acid copolymer (MA/AA), a dispersion scale inhibitor C, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (AA/AMPS) and a dispersion scale inhibitor D, sodium polyaspartate (PASP). The content of different components in the circulating water scale and corrosion inhibitor is adjusted according to the calcium-alkali ratio of the make-up water, so that an optimal formula suitable for the water quality is obtained, and the effect of the scale inhibitor is improved to the greatest extent.
Description
Technical Field
The invention relates to a method for adjusting a circulating water scale and corrosion inhibitor formula based on a make-up water calcium-base ratio, and belongs to the field of circulating water scale and corrosion inhibitor formulas.
Background
The scale and corrosion inhibitor treatment of the circulating cooling water mainly aims at the open circulating cooling water and aims at inhibiting the scaling and corrosion of a system. The scale and corrosion inhibitor is usually a compound formula, contains a plurality of medicaments, and can adopt different compounding proportions and dosages according to different water qualities and system conditions so as to obtain the optimal effect.
With the improvement of the national requirement on environmental protection and the promotion of recycling and secondary use of urban reclaimed water, more and more power plants are built, and urban reclaimed water of sewage treatment plants is used as a main water source, and a standby water source is surface water. In terms of water quality, sewage treatment plants have various treatment processes, large difference of operation management levels and frequent fluctuation of water quality of water supply. In terms of water quantity, urban reclaimed water is used as a priority water source, and when the water quantity is insufficient, the using amount of surface water is increased, so that the proportion of the urban reclaimed water and the surface water is changed. Therefore, the quality of the make-up water of the circulating cooling water system also changes greatly. According to the requirements of DL/T300-2011 thermal power plant condenser pipe anticorrosion and antiscale guide rules on circulating water operation control, when a water source is greatly changed, a circulating water dynamic simulation test, a screening and verification treatment process and an antiscale corrosion inhibitor are required to be carried out, and reasonable control parameters are determined.
However, in the current circulating water dynamic simulation test for screening the scale and corrosion inhibitor formula, circulating water make-up water in a certain short period of time on site is often used as test water, and the test result is used as a reference for circulating water operation control, so that the representativeness is not strong. In addition, the water quality is generally divided into negative hard water, temporary hard water and permanent hard water, and different agents have different effects in different water qualities, so that the formula is difficult to be the optimal formula under other water quality conditions.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for adjusting the formula of the circulating water scale and corrosion inhibitor on the basis of the calcium-alkali ratio of the make-up water, and the contents of different components in the agent are adjusted according to the calcium-alkali ratio of the make-up water so as to achieve the optimal formula suitable for the water quality and improve the action effect of the agent to the greatest extent.
In order to achieve the purpose, the invention adopts the technical scheme that:
a scale and corrosion inhibitor for circulating water comprises the following components in percentage by weight: organic phosphine scale inhibitor A: 0-1, dispersing type scale inhibitor B: 0-1, dispersing type scale inhibitor C: 0-1, dispersion type scale inhibitor D: 0-1, wherein the ratio is the ratio of the scale inhibitor of a single component to the total amount of the scale inhibitor A, B, C, D.
A is amino trimethylene phosphonic Acid (ATMP), B is maleic acid-acrylic acid copolymer (MA/AA), C is acrylic acid-2-acrylamide-2-methyl propane sulfonic acid copolymer (AA/AMPS), and D is Polyaspartic Acid Sodium (PASP).
Method for adjusting circulating water scale and corrosion inhibitor formula based on calcium-base ratio of make-up water, wherein calcium-base ratio is ratio of alkalinity to molar concentration of calcium ions, and JD/Ca is used2+Represents; JD/Ca2+The component content relationship with A, B, C, D is as follows:
A＝0.128+0.264(JD/Ca2+)-0.032(JD/Ca2+)2；
B＝0.702-0.284(JD/Ca2+)+0.043(JD/Ca2+)2-0.025/(JD/Ca2+)-0.05/(JD/Ca2+)2；
C＝0.337-0.257(JD/Ca2+)+0.09(JD/Ca2+)2-0.011(JD/Ca2+)3；
D＝0.483-0.168(JD/Ca2+)+0.022(JD/Ca2+)2-0.35/(JD/Ca2+)+0.121/(JD/Ca2+)2。
the method is applied to the regulation of a circulating water system.
The invention has the beneficial effects that:
the invention provides a circulating water scale and corrosion inhibitor which comprises an organic phosphine scale inhibitor A, aminotrimethylene phosphonic Acid (ATMP), a dispersion scale inhibitor B, a maleic acid-acrylic acid copolymer (MA/AA), a dispersion scale inhibitor C, an acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (AA/AMPS) and a dispersion scale inhibitor D, sodium polyaspartate (PASP). The content of different components in the circulating water scale and corrosion inhibitor is adjusted according to the calcium-alkali ratio of the make-up water, so that an optimal formula suitable for the water quality is obtained, and the effect of the scale inhibitor is improved to the greatest extent.
The method for adjusting the circulating water scale and corrosion inhibitor formula based on the make-up water calcium-base ratio is applied to the actual operation of the circulating water of the power plant, and the result shows that: the two units (2 multiplied by 660MW) circulating water systems run safely and stably, the end difference of the condenser is reduced by 1 degree on average, the coal consumption is reduced by about 0.3 percent, the coal-fired cost of the power plant is saved by about 300 ten thousand yuan each year, and the water intake of unit power generation is reduced by about 0.26m3And (MW & h), about 83 million tons of water can be saved every year, wherein the quantity of surface water taken is reduced by about 130 million tons, the quantity of reclaimed water in cities and towns is increased by about 47 million tons, the direct economic benefit is about 230 million yuan/year, and the additional economic benefit is 210 million yuan/year.
Drawings
FIG. 1 shows the ultimate carbonate hardness of organophosphine scale inhibitor monomers at different concentrations;
2, scale inhibition rates of 9 dispersed scale inhibitor monomers under different concentrations;
3, 6 scale inhibition rates of the dispersion scale inhibitor monomers under different concentrations;
FIG. 4, fraction A with JD/Ca2+The variation curve of (d);
FIG. 5, fraction B with JD/Ca2+The variation curve of (d);
FIG. 6, fraction C with JD/Ca2+The variation curve of (d);
FIG. 7, fraction D vs JD/Ca2+The variation curve of (d);
FIG. 8 shows the trend of the limiting concentration ratio of the make-up water of a certain power plant along with the change of the concentration of the chemical;
FIG. 9 is a dynamic simulation test of the variation trend of fouling thermal resistance of mixed water;
FIG. 10, JD (mmol/L) and JD + Ca2+(mg/L) as a function of time on stream.
Detailed Description
The following examples further illustrate the embodiments of the present invention in detail.
Example 1 screening of Scale inhibitor monomers
The information of the scale inhibitor used in the present invention is shown in Table 1.
Table 1 antiscalant information
| Serial number | Name (R) | Abbreviations | Form of the composition | |
| 1 | Amino trimethylene phosphonic acid | ATMP | Liquid, method for producing the same and use thereof | 50％ |
| 2 | Hydroxy ethylidene diphosphonic acid | HEDP | Liquid, method for producing the same and use thereof | 50％ |
| 3 | Ethylenediaminetetramethylenephosphonic acid | EDTMP | Liquid, method for producing the same and use thereof | 18-20％ |
| 4 | Polyaspartic acid sodium salt | PASP | Liquid, method for producing the same and use thereof | 40％ |
| 5 | Polyepoxysuccinic acid | PESA | Liquid, method for producing the same and use thereof | 40％ |
| 6 | Hydrolyzed polymaleic anhydride | HPMA | Liquid, method for producing the same and use thereof | 48％ |
| 7 | Maleic acid-acrylic acid copolymer | MA/AA | Liquid, method for producing the same and use thereof | 48％ |
| 8 | Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer | AA/AMPS | Liquid, method for producing the same and use thereof | 30％ |
| 9 | Imino disuccinic acid tetrasodium salt | IDS | Liquid, method for producing the same and use thereof | 33-35％ |
| 10 | Polyacrylic acid | PAA | Liquid, method for producing the same and use thereof | 30％ |
| 11 | Water-soluble chitosan | / | Solid body | 100％ |
| 12 | D-sodium gluconate | / | Solid body | 99％ |
Selecting an organic phosphine scale inhibitor monomer: aminotrimethylene phosphonic Acid (ATMP), hydroxyethylidene diphosphonic acid (HEDP) and ethylenediamine tetramethylene phosphonic acid (EDTMP) are subjected to a scale inhibition performance test of a scale inhibitor monomer by adopting a limit carbonate method, the evaluation index is limit carbonate hardness, and the test process refers to HG/T4541-2013 'determination limit carbonate method of scale inhibition performance of a water treatment agent'. The ultimate carbonate hardness of the organophosphine scale inhibitor monomer under different concentrations is measured, and the test result is shown in figure 1. As can be seen from FIG. 1, ATMP has a superior scale inhibition effect to HEDP and EDTMP.
Selecting a dispersing scale inhibitor monomer: the scale inhibition performance test of the scale inhibitor monomer is carried out by adopting a calcium carbonate deposition method, wherein the evaluation index is scale inhibition rate, and the test process refers to GB/T16632-. And (3) measuring the scale inhibition rate of the dispersion scale inhibitor monomer under different concentrations, wherein the test result is shown in figure 2.
As can be seen from fig. 2, the scale inhibition ratio of the dispersed scale inhibitor monomer increases as the concentration increases. The scale inhibition rate of IDS, water-soluble chitosan and D-sodium gluconate at the current concentration is far lower than that of the other six scale inhibition dispersion monomer monomers. The data for these six scale inhibitors are plotted separately, as shown in figure 3.
As can be clearly seen from fig. 3, the dispersed scale inhibitor monomer PASP has a higher scale inhibition rate at a low dosage. When the dispersion scale inhibitor monomer PESA is in a higher dosage, the scale inhibition rate is obviously improved, but the dispersion scale inhibitor monomer PESA tends to be stable after reaching a certain value. When the concentration of the dispersion scale inhibitor monomer HPMA, MA/AA, AA/AMPS and PAA is more than 8mg/L, the scale inhibition rate is obviously and slowly increased, and the scale inhibition rate is 55 to 70 percent, and the difference is small.
According to the screening experiment result of the scale inhibitor monomer and the certain similarity of the scale inhibitors in structure, the organic phosphine scale inhibitor monomer ATMP, the dispersion scale inhibitor monomer MA/AA, the dispersion scale inhibitor monomer AA/AMPS and the dispersion scale inhibitor monomer PASP are screened out for carrying out the compounding experiment.
Example 2 screening of Scale inhibitor formulations
A, B, C, D respectively represent an organic phosphine scale inhibitor monomer ATMP, a dispersion scale inhibitor monomer MA/AA, a dispersion scale inhibitor monomer AA/AMPS and a dispersion scale inhibitor monomer PASP, and the scheme is as follows:
(1) the boundaries of the respective scale inhibitor ratios (compounding amounts, i.e., the ratio of the single scale inhibitor to the total amount of scale inhibitor) were determined as shown in table 2.
TABLE 2 ratio ranges of the respective antiscalants
(2) The material mixing uniformity test using the simplex gravity center design is shown in table 3.
TABLE 3 test design Table
| Numbering | A | | C | D | |
| 1 | 1 | 0 | 0 | 0 | |
| 2 | 0 | 1 | 0 | 0 | |
| 3 | 0 | 0 | 1 | 0 | |
| 4 | 0 | 0 | 0 | 1 | |
| 5 | 0.5 | 0.5 | 0 | 0 | |
| 6 | 0.5 | 0 | 0.5 | 0 | |
| 7 | 0.5 | 0 | 0 | 0.5 | |
| 8 | 0 | 0.5 | 0.5 | 0 | |
| 9 | 0 | 0.5 | 0 | 0.5 | |
| 10 | 0 | 0 | 0.5 | 0.5 | |
| 11 | 0.33 | 0.33 | 0.33 | 0 | |
| 12 | 0.33 | 0.33 | 0 | 0.33 | |
| 13 | 0.33 | 0 | 0.33 | 0.33 | |
| 14 | 0 | 0.33 | 0.33 | 0.33 | |
| 15 | 0.25 | 0.25 | 0.25 | 0.25 |
Note that the ratio of 0.33 in the table represents the ratio of individual to total amount of scale inhibitor 1/3, as shown in the table below.
(3) According to the proportion of each component in the test design table, referring to HG/T4541-2013 'limit carbonate method for determining scale inhibition performance of water treatment agent', a limit carbonate method scale inhibition performance test is carried out, and test water respectively represents negative hard water (the alkalinity is larger than the hardness) and temporary hard water (the alkalinity is larger than the hardness) with different calcium-alkali ratios (the ratio of the alkalinity to the calcium ion concentration) as shown in Table 4Equal to hardness), permanent hard water (alkalinity less than hardness), where alkalinity (JD) represents the total amount of all species in the water that can undergo a neutralization reaction with a strong acid, i.e., NaHCO in table 4 below3The concentration of (c); hardness represents Ca in water2+、Mg2+The content of ions, i.e. CaCl in Table 4 below2The concentration of (c).
TABLE 4 test waters
Wherein, JD/Ca2+Represents: NaHCO 23(mmol/L) with CaCl2Ratio of (mmol/L)
(4) The test results are shown in tables 5, 6, 7, 8, 9, 10 and 11, respectively.
TABLE 5 test results of test Water 1
The regression equation is of the form:
Klim＝1.61-0.95A-0.06B+0.58D+2.58AB+4.9AC+0.14AD+1.8BC-2.56BD-2.72CD-2.151ABC-26.311ABD-29.79ACD-19.273BCD+494.097ABCD
when a is 0.25, B is 0.27, C is 0.24, and D is 0.24, Δ K is obtained by using a plan solving toollimObtaining the maximum value and calculating the value delta Klim(max) was 2.50.
According to Δ KlimWhen the maximum value is obtained, A, B, C, D component content is used to obtain verification value delta KlimWas 2.47.
TABLE 6 test results of test Water 2
The regression equation is of the form:
Klim＝1.29-0.4A+0.39B+1.18D+2.42AB+5.72AC-0.68AD+3.54BC-6.02BD-4.16CD-5.806ABC+13.078ABD-27.082ACD-8.487BCD+352.867ABCD
when a is 0.28, B is 0.38, C is 0.20, and D is 0.14, Δ K is obtained by using a plan solving toollimObtaining the maximum value and calculating the value delta Klim(max) was 2.69.
According to Δ KlimWhen the maximum value is obtained, A, B, C, D component content is used to obtain verification value delta KlimIs 2.68.
TABLE 7 test results of test Water 3
The regression equation is of the form:
Klim＝1.19-0.36A+0.57B+1.28D+2.86AB+6.72AC-0.16AD+4.26BC-6.06BD-3.8CD-0.18ABC+40.465ABD-30.725ACD-9.201BCD+185.124ABCD
when a is 0.32, B is 0.39, C is 0.19, and D is 0.10, Δ K is obtained by using a plan solving toollimObtaining the maximum value and calculating the value delta Klim(max) was 2.88.
According to Δ KlimWhen the maximum value is obtained, A, B, C, D component content is used to obtain verification value delta KlimIs 2.85.
Table 8 test results of test water 4
The regression equation is of the form:
Klim＝1+0.65A+0.96B+1.52D+1.46AB+6.3AC+0.22AD+4.16BC-6.2BD-3.28CD+4.748ABC+42.834ABD-35.867ACD-8.6BCD+205.459ABCD
when a is 0.39, B is 0.36, C is 0.14, and D is 0.11, Δ K is obtained by using a plan solving toollimObtaining the maximum value and calculating the value delta Klim(max) was 3.17.
According to Δ KlimWhen the maximum value is obtained, A, B, C, D component content is used to obtain verification value delta KlimIs 3.18.
TABLE 9 test results for test Water 5
The regression equation is of the form:
Klim＝1.12+2.09A+0.73B+0.95D+1.68AB+3.7AC+0.12AD+4.14BC-5.32BD-2.74CD+7.309ABC+36.431ABD-33.971ACD-9.67BCD+155.442ABCD
when a is 0.46, B is 0.34, C is 0.10, and D is 0.10, Δ K is obtained by using a plan solving toollimObtaining the maximum value and calculating the value delta Klim(max) was 3.53.
According to Δ KlimWhen the maximum value is obtained, A, B, C, D component content is used to obtain verification value delta KlimIs 3.50.
TABLE 10 test results for test Water 6
The regression equation is of the form:
Klim＝1.3+2.46A+0.49B+0.81D+3.22AB+4.04AC+0.5AD+5.34BC-4.8BD-2.78CD+3.739ABC+36.364ABD-38.144ACD-13.219BCD+153.841ABCD
using a plan solving tool, when a is 0.58, B is 0.25, C is 0.09, and D is 0.08, Δ K is obtainedlimObtaining the maximum value, calculated by Δ Klim(max) was 4.07.
According to Δ KlimWhen the maximum value is obtained, A, B, C, D component content is used to obtain verification value delta KlimIt was 4.09.
TABLE 11 test results of test Water 7
The regression equation is of the form:
Klim＝1.35+3.19A+0.68B+0.78D+4.1AB+4.7AC+1.42AD+6.32BC-4.6BD-1.96CD+3.237ABC+37.435ABD-46.001ACD-15.749BCD+118.515ABCD
when a is 0.65, B is 0.22, C is 0.06, and D is 0.07, Δ K is obtained by using a planning toollimObtaining the maximum value and calculating the value delta Klim(max) was 4.80.
According to Δ KlimWhen the maximum value is obtained, A, B, C, D component content is used to obtain verification value delta KlimIt was 4.77.
(5) Calcium to base ratio (JD/Ca)2+) Component content relation with A, B, C, D
According to the test results of the above test waters 1 to 7,. DELTA.K was obtainedlimThe relationship between the content of A, B, C, D components and the calcium-base ratio (JD/Ca) is taken as the maximum value2+) The relationship between the amounts of the components and A, B, C, D is shown in Table 12.
TABLE 12 JD/Ca2+Component content relation with A, B, C, D
| Numbering | JD/Ca2+ | A | B | C | |
| Test Water | |||||
| 1 | 0.44 | 0.25 | 0.27 | 0.24 | 0.24 |
| |
0.63 | 0.28 | 0.38 | 0.2 | 0.14 |
| Test Water 3 | 0.86 | 0.32 | 0.39 | 0.19 | 0.1 |
| |
1.17 | 0.39 | 0.36 | 0.14 | 0.11 |
| |
1.60 | 0.46 | 0.34 | 0.1 | 0.1 |
| |
2.25 | 0.58 | 0.25 | 0.09 | 0.08 |
| Test Water 7 | 3.33 | 0.65 | 0.22 | 0.06 | 0.07 |
The calcium to base ratio (JD/Ca) of component A is obtained from Table 122+) See fig. 4.
The regression equation is of the form: a ═ 0.128+0.264 (JD/Ca)2+)-0.032(JD/Ca2+)2
The model was examined as shown in Table 13.
TABLE 13 summary of models
Wherein, the meaning of R is a correlation coefficient, and the degree of correlation of the independent variable and the dependent variable fluctuation is provided with direction and magnitude; r2The reaction regression equation can explain the degree of the sum of squared deviations and the sum of squared deviations, and the value of the sum of squared deviations is equal to the square of the correlation coefficient R; adjusting R2The square R needs to be adjusted to account for overestimating the square R for the added independent variable. The larger the difference between the adjusted R square and the R square, the worse the fitting of the model.
Component B with calcium to base ratio (JD/Ca)2+) See fig. 5.
The regression equation is of the form:
B＝0.702-0.284(JD/Ca2+)+0.043(JD/Ca2+)2-0.025/(JD/Ca2+)-0.05/(JD/Ca2+)2
the model was examined as shown in Table 14.
Table 14 model summary
Component C with calcium to base ratio (JD/Ca)2+) See fig. 6.
The regression equation is of the form: c-0.337-0.257 (JD/Ca)2+)+0.09(JD/Ca2+)2-0.011(JD/Ca2+)3
The model was examined as shown in Table 15.
Table 15 summary of models
Component D with calcium to base ratio (JD/Ca)2+) See fig. 7.
The regression equation is of the form:
D＝0.483-0.168(JD/Ca2+)+0.022(JD/Ca2+)2-0.35/(JD/Ca2+)+0.121/(JD/Ca2+)2
the model was examined as shown in Table 16.
TABLE 16 summary of models
Example 3 method of adjusting Scale inhibitor formulation
The formula of the circulating water scale and corrosion inhibitor is adjusted on the basis of the calcium-alkali ratio of the make-up water. The replenishing water of a certain power plant has two water sources of surface water and urban reclaimed water, the water volume of the urban reclaimed water is not fixed, so that the proportion of the surface water and the urban reclaimed water in the replenishing water is changed greatly daily, and the quality analysis of the replenishing water is shown in a table 17.
TABLE 17 analysis of make-up water quality of a power plant
| Detecting items | Surface water | Effluent of reclaimed water treatment system |
| Turbidity (NTU) | 0.97 | 1.42 |
| Conductivity (μ S/cm) | 698 | 1121 |
| pH | 8.0 | 8.1 |
| Phenolphthalein basicity (mmol/L) | 0 | 0 |
| Total alkalinity (mmol/L) | 2.76 | 2.15 |
| Ca2+(with CaCO)3Meter) (mg/L) | 98 | 350 |
| Total hardness (as CaCO)3Meter) (mg/L) | 202 | 400 |
| COD (in terms of O)2Meter) (mg/L) | 13 | 28.8 |
| Cl-(mg/L) | 61.4 | 86.7 |
| SO4 2-(mg/L) | 117 | 180.1 |
According to the requirement of the power plant circulating water for water supplement, the surface water and the effluent of the reclaimed water treatment system are mixed according to the ratio of 1:0, 3:1, 2:2, 1:3 and 0:1, and the water quality index of the mixed water before concentration is shown in a table 18.
TABLE 18 Water quality index of the Water mixture before concentration
As can be seen from Table 18, as the ratio of surface water to reclaimed water in the effluent of the water treatment system changes, the mixed water gradually changes from negative hard water to permanent hard water according to the calcium-base ratio (JD/Ca)2+) And (3) adjusting the component content of A, B, C, D in the scale inhibitor formula in relation to the component content of A, B, C, D.
For #1 mix water:
JD/Ca2+the content of component A, B, C, D in the scale inhibitor was determined according to the test results of example 2, respectively. Namely: a ═ 0.128+0.264 (JD/Ca)2+)-0.032(JD/Ca2+)2，A＝0.62；
B＝0.702-0.284(JD/Ca2+)+0.043(JD/Ca2+)2-0.025/(JD/Ca2+)-0.05/(JD/Ca2+)2，B＝0.23；
C＝0.337-0.257(JD/Ca2+)+0.09(JD/Ca2+)2-0.011(JD/Ca2+)3，C＝0.08；
D＝0.483-0.168(JD/Ca2+)+0.022(JD/Ca2+)2-0.35/(JD/Ca2+)+0.121/(JD/Ca2+)2，D＝0.08。
For #2 mix water:
JD/Ca2+the content of component A, B, C, D in the scale inhibitor was determined according to the test results of example 2, 1.62, respectively. Namely: a ═ 0.128+0.264 (JD/Ca)2+)-0.032(JD/Ca2+)2，A＝0.47；
B＝0.702-0.284(JD/Ca2+)+0.043(JD/Ca2+)2-0.025/(JD/Ca2+)-0.05/(JD/Ca2+)2，B＝0.32；
C＝0.337-0.257(JD/Ca2+)+0.09(JD/Ca2+)2-0.011(JD/Ca2+)3，C＝0.11；
D＝0.483-0.168(JD/Ca2+)+0.022(JD/Ca2+)2-0.35/(JD/Ca2+)+0.121/(JD/Ca2+)2，D＝0.10。
For #3 mix water:
JD/Ca2+the content of component A, B, C, D in the scale inhibitor was determined according to the test results of example 2, 1.10, respectively. Namely: a ═ 0.128+0.264 (JD/Ca)2+)-0.032(JD/Ca2+)2，A＝0.38；
B＝0.702-0.284(JD/Ca2+)+0.043(JD/Ca2+)2-0.025/(JD/Ca2+)-0.05/(JD/Ca2+)2，B＝0.38；
C＝0.337-0.257(JD/Ca2+)+0.09(JD/Ca2+)2-0.011(JD/Ca2+)3，C＝0.15；
D＝0.483-0.168(JD/Ca2+)+0.022(JD/Ca2+)2-0.35/(JD/Ca2+)+0.121/(JD/Ca2+)2，D＝0.11。
For #4 mix water:
JD/Ca2+the content of component A, B, C, D in the scale inhibitor was determined according to the test results of example 2, 0.80, respectively. Namely: a ═ 0.128+0.264 (JD/Ca)2+)-0.032(JD/Ca2+)2，A＝0.32；
B＝0.702-0.284(JD/Ca2+)+0.043(JD/Ca2+)2-0.025/(JD/Ca2+)-0.05/(JD/Ca2+)2，B＝0.39；
C＝0.337-0.257(JD/Ca2+)+0.09(JD/Ca2+)2-0.011(JD/Ca2+)3，C＝0.18；
D＝0.483-0.168(JD/Ca2+)+0.022(JD/Ca2+)2-0.35/(JD/Ca2+)+0.121/(JD/Ca2+)2，D＝0.11。
For #5 mix water:
JD/Ca2+the content of component A, B, C, D in the scale inhibitor was determined according to the test results of example 2, 0.61, respectively. Namely:
A＝0.128+0.264(JD/Ca2+)-0.032(JD/Ca2+)2，A＝0.28；
B＝0.702-0.284(JD/Ca2+)+0.043(JD/Ca2+)2-0.025/(JD/Ca2+)-0.05/(JD/Ca2+)2，B＝0.37；
C＝0.337-0.257(JD/Ca2+)+0.09(JD/Ca2+)2-0.011(JD/Ca2+)3，C＝0.21；
D＝0.483-0.168(JD/Ca2+)+0.022(JD/Ca2+)2-0.35/(JD/Ca2+)+0.121/(JD/Ca2+)2，D＝0.14。
application example 1 determining scale and corrosion inhibitor formula according to make-up water calcium-base ratio
The water quality index of the make-up water of a certain power plant is shown in a table 19.
TABLE 19 Water quality index of make-up water of a certain power plant
| Item | Numerical value | Item | Numerical value |
| pH | 7.92 | HCO3 -(mmol/L) | 3.82 |
| Conductivity (25 ℃ C.) (μ S/cm) | 1876 | Phenolphthalein basicity (mmol/L) | 0.0 |
| Cl-1(mg/L) | 234.0 | Total alkalinity (mmol/L) | 3.82 |
| SO4 2-(mg/L) | 278.0 | 1/2 Total hardness (mmol/L) | 5.22 |
| CO3 2-(mg/L) | 0.0 | 1/2 temporary hardness (mmol/L) | 3.82 |
| Ca2+(mg/L) | 55.2 | 1/2 permanent hardness (mmol/L) | 0.0 |
| Mg2+(mg/L) | 29.5 | SiO2mg/L (all silicon) | / |
JD/Ca2+2.77 in terms of calcium-base ratio (JD/Ca)2+) And determining the content of the component A, B, C, D in the scale inhibitor respectively according to a relation curve of the component content of A, B, C, D. Namely:
A＝0.128+0.264(JD/Ca2+)-0.032(JD/Ca2+)2，A＝0.61；
B＝0.702-0.284(JD/Ca2+)+0.043(JD/Ca2+)2-0.025/(JD/Ca2+)-0.05/(JD/Ca2+)2，B＝0.23；
C＝0.337-0.257(JD/Ca2+)+0.09(JD/Ca2+)2-0.011(JD/Ca2+)3，C＝0.07；
D＝0.483-0.168(JD/Ca2+)+0.022(JD/Ca2+)2-0.35/(JD/Ca2+)+0.121/(JD/Ca2+)2，D＝0.09。
preparing the scale and corrosion inhibitor according to the proportion of the components, carrying out a scale inhibition performance test of the extreme carbonate method in 2020 by referring to HG/T4541-2013 ' determination extreme carbonate method for scale inhibition performance of water treatment agent ', and controlling the calcium hardness and alkalinity concentration in the circulating cooling water by CaCO according to GB/T50050-2017 ' design specification for treatment of industrial circulating cooling water3Counting; in the water quality analysis table of the measurement items, the hardness and basicity of calcium are generally measured in mmol/L, and the basicity is 1mmol/L to 50mg/L (as CaCO)3Calculated), calcium hardness 1 mmol/L-100 mg/L (as CaCO)3Meter). The test results are shown in tables 20, 21, 22, 23, 24, 25 and 8.
TABLE 20 static limit carbonate blank test for make-up water of a certain power plant
Wherein, KJDIs the ratio of the alkalinity value in water after raw water concentration to the alkalinity value in raw water, KCLThe ratio of the concentration of chloride ions in the water after the raw water is concentrated to the concentration of chloride ions in the raw water, and Delta A is KCL -And KJDWhen the difference value of delta A is more than or equal to 0.2, the circulating water is scaled. The following table is the same.
TABLE 21 static limit carbonate test for supplementing water to a power plant (dosage 8mg/L)
TABLE 22 static limit carbonate test for water make-up in a certain power plant (dosage 10mg/L)
TABLE 23 static limit carbonate test for water make-up in a certain power plant (dosage 12mg/L)
TABLE 24 static limit carbonate test for supplementing water to a power plant (14 mg/L dosage)
TABLE 25 static limit carbonate test for supplementing water to a power plant (dosage 16mg/L)
From a test knotAccording to the results, when the concentration of the scale and corrosion inhibitor is below 12mg/L, the concentration ratio of the static limit carbonate of the water sample is increased along with the concentration of the medicament (when the delta A is more than or equal to 0.2, K isCl-The value of (2) is the concentration ratio of the limiting carbonate) is obviously increased, the concentration of the scale and corrosion inhibitor is increased continuously along with the concentration of the medicament after being more than 12mg/L, the concentration ratio of the static limiting carbonate of the water sample is hardly increased, so that the concentration ratio of the scale and corrosion inhibitor in the supplementing water is 12mg/L which is the optimal concentration, the concentration ratio of the water sample is 3.11, the hardness of the limiting carbonate reaches 12mmol/L, compared with the common scale and corrosion inhibitor, the hardness of the carbonate of 7-8 mmol/L can be stabilized, the scale inhibition performance of the compounded medicament is excellent, and compared with the common medicament, the scale inhibition effect is improved by more than 30%.
Application example 2 application of formula adjustment method of scale inhibitor
With reference to HG/T2160-. The results of the dynamic simulation test of the mixed water are shown in Table 26. Wherein, full alkalinity: 1mmol ═ 50mg/L (as CaCO)3Calculated as total alkalinity 2.76mmol/L, calcium hardness 98mg/L (calculated as CaCO)3Calculated), then calcium hardness + full alkalinity (as CaCO)3Calculated as (2.76X 50+98) mg/L (236 mg/L) as CaCO3Meter).
TABLE 26 dynamic simulation test results of mixed water
The variation trend of fouling resistance of the mixed water dynamic simulation test is shown in figure 9. From the results of the dynamic simulation test, it is known that when the concentration of the scale and corrosion inhibitor added to the mixed water is 8mg/L, and the circulating water make-up water is changed to the mixed water of #1, #5, #3, #2 and #4 in sequence, the fouling resistance increases slowly, and after 16 days of operation, the fouling resistance is stabilized at about 1.40, and at this time, the fouling deposition rate and the stripping rate are approximately equal. The thermal resistance value of dirt on the water side of the equipment heat transfer surface in GB/T50050 plus 2017 Industrial circulating cooling water treatment design Specification should not be more than 3.44 multiplied by 10-4m2The requirement of K/W indicates that the compatibility of the compound medicament is excellent under different water qualities.
Circulating water alkalinity (mmol/L), calcium hardness + full alkalinity (as CaCO)3Meter) versus run time is shown in fig. 10.
When the circulating water make-up water is #1 mixed water, the calcium hardness of the circulating water is plus the full alkalinity (with CaCO)3Calculated) should be controlled to be 962-990 mg/L, and the total alkalinity should be controlled to be below 11.35 mmol/L.
When the circulating water make-up water is #5 mixed water, the calcium hardness of the circulating water is plus the full alkalinity (with CaCO)3In terms of the total alkalinity, the total alkalinity is controlled to be 1715-1750 mg/L and below 8.25 mmol/L.
When the circulating water make-up water is #3 mixed water, the calcium hardness of the circulating water is plus the full alkalinity (with CaCO)3Designed) should be controlled at 1320-1350 mg/L, and the total alkalinity should be controlled below 9.35 mmol/L.
When the circulating water make-up water is #2 mixed water, the calcium hardness of the circulating water is plus the full alkalinity (with CaCO)3In terms of) should be controlled to be 1130-1170 mg/L, and the total alkalinity should be controlled to be below 10.26 mmol/L.
When the circulating water make-up water is mixed water # 4, the calcium hardness of the circulating water is plus the full alkalinity (using CaCO3Calculated) should be controlled to be 1490-1540 mg/L, and the total alkalinity should be controlled to be below 8.69 mmol/L.
Compared with the common scale and corrosion inhibitor, the hardness of 7-8 mmol/L carbonate is stable, and the compounded medicament has excellent scale inhibition performance. In addition, when the make-up water is switched to the mixed water of different ratios, the control index of circulating water changes correspondingly, not only furthest promotes the concentration multiple of circulating water, effectively avoids condenser pipe scale deposit moreover.
The scale inhibitor formula adjustment method based on the calcium-alkali ratio of the make-up water is successfully applied to a plurality of power plants, and the result shows that: the two units (2 multiplied by 660MW) circulating water systems run safely and stably, the end difference of the condenser is reduced by 1 degree on average, the coal consumption is reduced by about 0.3 percent, the coal-fired cost of the power plant is saved by about 300 ten thousand yuan each year, and the water intake of unit power generation is reduced by about 0.26m3And (MW & h), about 83 million tons of water can be saved every year, wherein the quantity of surface water taken is reduced by about 130 million tons, the quantity of reclaimed water in cities and towns is increased by about 47 million tons, the direct economic benefit is about 230 million yuan/year, and the additional economic benefit is 210 million yuan/year.
Claims (4)
1. The circulating water scale and corrosion inhibitor is characterized by comprising the following components in percentage by weight: organic phosphine scale inhibitor A: 0-1, dispersing type scale inhibitor B: 0-1, dispersing type scale inhibitor C: 0-1, dispersion type scale inhibitor D: 0-1, wherein the ratio is the ratio of the scale inhibitor of a single component to the total amount of the scale inhibitor A, B, C, D.
2. The circulating water scale and corrosion inhibitor of claim 1, wherein A is aminotrimethylene phosphonic Acid (ATMP), B is maleic acid-acrylic acid copolymer (MA/AA), C is acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (AA/AMPS), and D is sodium polyaspartate (PASP).
3. A method for adjusting the circulating water scale and corrosion inhibitor formulation according to claim 1 or 2 based on the calcium-base ratio of the make-up water, wherein the calcium-base ratio is the ratio of alkalinity to the molar concentration of calcium ions, JD/Ca is used2+Represents; JD/Ca2+The component content relationship with A, B, C, D is as follows:
A＝0.128+0.264(JD/Ca2+)-0.032(JD/Ca2+)2；
B＝0.702-0.284(JD/Ca2+)+0.043(JD/Ca2+)2-0.025/(JD/Ca2+)-0.05/(JD/Ca2+)2；
C＝0.337-0.257(JD/Ca2+)+0.09(JD/Ca2+)2-0.011(JD/Ca2+)3；
D＝0.483-0.168(JD/Ca2+)+0.022(JD/Ca2+)2-0.35/(JD/Ca2+)+0.121/(JD/Ca2+)2。
4. use of the method according to claim 3 for the conditioning of a circulating water system.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114159976A (en) * | 2021-09-24 | 2022-03-11 | 南京开广化工有限公司 | Reverse osmosis scale inhibitor and preparation method thereof |
| CN115321722A (en) * | 2022-08-31 | 2022-11-11 | 中国大唐集团科学技术研究院有限公司中南电力试验研究院 | Chemical agent coupling electrochemical treatment device for circulating cooling water system |
| CN116657128A (en) * | 2023-07-31 | 2023-08-29 | 杭州尚善若水环保科技有限公司 | Phosphorus-free prefilming combined reagent and circulating water phosphorus-free combined prefilming treatment method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0511850A1 (en) * | 1991-04-30 | 1992-11-04 | Calgon Corporation | Terpolymer of itaconic acid for high PH scale control |
| JPH0994598A (en) * | 1995-09-29 | 1997-04-08 | Kurita Water Ind Ltd | Corrosionproof and scale-proof method of open circulating cooling water system |
| CN1785853A (en) * | 2004-12-10 | 2006-06-14 | 中国石化北京燕化石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application in water treatment |
| CN101412568A (en) * | 2008-10-31 | 2009-04-22 | 河北省电力研究院 | Scale inhibitor for circulating water |
| CA2689830A1 (en) * | 2009-01-12 | 2010-07-12 | Daniel D. Duarte | Method to inhibit scale formation in cooling circuits using carbon dioxide |
| CN101913712A (en) * | 2009-07-22 | 2010-12-15 | 乌鲁木齐市科发展精细化工有限公司 | Low-phosphorous environment-friendly scale inhibitor adapting to 'three-high' water quality and preparation thereof |
| CN110980972A (en) * | 2019-12-18 | 2020-04-10 | 中国大唐集团科学技术研究院有限公司华中电力试验研究院 | Scale inhibition and dispersion agent and calculation method and application of universal limit concentration multiple of circulating cooling water of scale inhibition and dispersion agent |
-
2021
- 2021-05-28 CN CN202110588957.2A patent/CN113248032B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0511850A1 (en) * | 1991-04-30 | 1992-11-04 | Calgon Corporation | Terpolymer of itaconic acid for high PH scale control |
| JPH0994598A (en) * | 1995-09-29 | 1997-04-08 | Kurita Water Ind Ltd | Corrosionproof and scale-proof method of open circulating cooling water system |
| CN1785853A (en) * | 2004-12-10 | 2006-06-14 | 中国石化北京燕化石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application in water treatment |
| CN101412568A (en) * | 2008-10-31 | 2009-04-22 | 河北省电力研究院 | Scale inhibitor for circulating water |
| CA2689830A1 (en) * | 2009-01-12 | 2010-07-12 | Daniel D. Duarte | Method to inhibit scale formation in cooling circuits using carbon dioxide |
| CN101913712A (en) * | 2009-07-22 | 2010-12-15 | 乌鲁木齐市科发展精细化工有限公司 | Low-phosphorous environment-friendly scale inhibitor adapting to 'three-high' water quality and preparation thereof |
| CN110980972A (en) * | 2019-12-18 | 2020-04-10 | 中国大唐集团科学技术研究院有限公司华中电力试验研究院 | Scale inhibition and dispersion agent and calculation method and application of universal limit concentration multiple of circulating cooling water of scale inhibition and dispersion agent |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114159976A (en) * | 2021-09-24 | 2022-03-11 | 南京开广化工有限公司 | Reverse osmosis scale inhibitor and preparation method thereof |
| CN115321722A (en) * | 2022-08-31 | 2022-11-11 | 中国大唐集团科学技术研究院有限公司中南电力试验研究院 | Chemical agent coupling electrochemical treatment device for circulating cooling water system |
| CN115321722B (en) * | 2022-08-31 | 2024-03-29 | 中国大唐集团科学技术研究院有限公司中南电力试验研究院 | Chemical agent coupling electrochemical treatment device for circulating cooling water system |
| CN116657128A (en) * | 2023-07-31 | 2023-08-29 | 杭州尚善若水环保科技有限公司 | Phosphorus-free prefilming combined reagent and circulating water phosphorus-free combined prefilming treatment method |
| CN116657128B (en) * | 2023-07-31 | 2023-10-03 | 杭州尚善若水环保科技有限公司 | Phosphorus-free prefilming combined reagent and circulating water phosphorus-free combined prefilming treatment method |
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