CN113248032B - Method for adjusting circulating water scale and corrosion inhibitor formula based on supplementing water calcium-alkali ratio - Google Patents
Method for adjusting circulating water scale and corrosion inhibitor formula based on supplementing water calcium-alkali ratio Download PDFInfo
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- 230000007797 corrosion Effects 0.000 title claims abstract description 30
- 238000005260 corrosion Methods 0.000 title claims abstract description 30
- 239000003112 inhibitor Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 25
- 239000003513 alkali Substances 0.000 title claims abstract description 24
- 239000011575 calcium Substances 0.000 claims abstract description 175
- 239000002455 scale inhibitor Substances 0.000 claims abstract description 69
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 29
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- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims abstract description 13
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- JPZROSNLRWHSQQ-UHFFFAOYSA-N furan-2,5-dione;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1OC(=O)C=C1 JPZROSNLRWHSQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 8
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims abstract description 6
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
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- 239000000178 monomer Substances 0.000 description 25
- 230000005764 inhibitory process Effects 0.000 description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 20
- 239000007788 liquid Substances 0.000 description 10
- 239000002352 surface water Substances 0.000 description 10
- 238000005094 computer simulation Methods 0.000 description 9
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- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000008233 hard water Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
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- 230000008859 change Effects 0.000 description 6
- 229920001529 polyepoxysuccinic acid Polymers 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 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 4
- 230000008569 process Effects 0.000 description 4
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 3
- 229940120146 EDTMP Drugs 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 3
- 229940080260 iminodisuccinate Drugs 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- GYBINGQBXROMRS-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)NC(C([O-])=O)CC([O-])=O GYBINGQBXROMRS-UHFFFAOYSA-J 0.000 description 2
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DDAQLPYLBPPPRV-UHFFFAOYSA-N [4-(hydroxymethyl)-2-oxo-1,3,2lambda5-dioxaphosphetan-2-yl] dihydrogen phosphate Chemical compound OCC1OP(=O)(OP(O)(O)=O)O1 DDAQLPYLBPPPRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 238000007726 management method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- UPMFZISCCZSDND-JJKGCWMISA-M sodium gluconate Chemical compound [Na+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O UPMFZISCCZSDND-JJKGCWMISA-M 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- MSXHSNHNTORCAW-GGLLEASOSA-M sodium;(2s,3s,4s,5r,6s)-3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].O[C@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O MSXHSNHNTORCAW-GGLLEASOSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 229940080258 tetrasodium iminodisuccinate Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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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
- C02F5/14—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 containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to a method for adjusting a circulating water scale and corrosion inhibitor formula based on a supplementing water calcium-alkali ratio, wherein the circulating water scale and corrosion inhibitor comprises an organic phosphine scale inhibitor A amino trimethylene phosphonic Acid (ATMP), a dispersing scale inhibitor B maleic acid-acrylic acid copolymer (MA/AA), a dispersing scale inhibitor C acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (AA/AMPS) and a dispersing scale inhibitor D sodium polyaspartate (PASP). According to the ratio of the calcium and the alkali in the supplementing water, the contents of different components in the circulating water scale and corrosion inhibitor are adjusted, so that an optimal formula suitable for the water quality is obtained, and the action 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 the ratio of calcium and alkali in supplementing water, belonging to the field of circulating water scale and corrosion inhibitor formulas.
Background
The scale and corrosion inhibitor treatment of circulating cooling water is mainly aimed at open-type circulating cooling water, and aims at inhibiting scaling and corrosion of the system. The scale and corrosion inhibitor is often a compound formulation and contains a plurality of medicaments, and different compounding proportions and dosages can be adopted for different water quality and system conditions so as to obtain the best effect.
Along with the improvement of the national environmental protection requirements and the promotion of secondary use of urban reclaimed water recovery, more and more built power plants take urban reclaimed water of sewage treatment plants as a main water source and standby water sources as surface water. In terms of water quality, sewage treatment plants have various treatment processes, large running management level differences and frequent water quality fluctuation 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 consumption of surface water is increased, so that the ratio of the urban reclaimed water to the surface water is changed. Thus, the quality of the make-up water of the recirculating cooling water system also changes significantly. According to the requirements of DL/T300-2011 on the running control of circulating water, when the water source is greatly changed, a circulating water dynamic simulation test is required to be carried out, and a treatment process and a scale and corrosion inhibitor are screened and verified to determine reasonable control parameters.
However, the current circulating water dynamic simulation test for screening the scale and corrosion inhibitor formula often adopts circulating water supplementing water in a certain short period of time on site as test water, and the test result is used as a reference for controlling the running of the circulating water, so that the representativeness is not strong. In addition, water quality is generally divided into negative hard water, temporary hard water and permanent hard water, and different agents show 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 based on the ratio of the supplementing water to the calcium and the alkali, and the contents of different components in the agent are adjusted according to the ratio of the supplementing water to the calcium and the alkali, so that the optimal formula suitable for the water quality is achieved, and the action effect of the agent is improved to the greatest extent.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the circulating water scale and corrosion inhibitor comprises the following components in percentage by weight: organic phosphine scale inhibitor A:0 to 1, a dispersion scale inhibitor B:0 to 1, a dispersion scale inhibitor C:0 to 1, a dispersion scale inhibitor D:0 to 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-methylpropanesulfonic acid copolymer (AA/AMPS), D is sodium polyaspartate (PASP).
The method for regulating the formulation of the circulating water scale and corrosion inhibitor based on the ratio of calcium and alkali in the supplementing water, wherein the ratio of the calcium and alkali is the ratio of the molar concentration of alkalinity to calcium ions, and JD/Ca is used 2+ A representation; JD/Ca 2+ The content relation of the components with A, B, C, D is as follows:
A＝0.128+0.264(JD/Ca 2+ )-0.032(JD/Ca 2+ ) 2 ；
B＝0.702-0.284(JD/Ca 2+ )+0.043(JD/Ca 2+ ) 2 -0.025/(JD/Ca 2+ )-0.05/(JD/Ca 2+ ) 2 ；
C＝0.337-0.257(JD/Ca 2+ )+0.09(JD/Ca 2+ ) 2 -0.011(JD/Ca 2+ ) 3 ；
D＝0.483-0.168(JD/Ca 2+ )+0.022(JD/Ca 2+ ) 2 -0.35/(JD/Ca 2+ )+0.121/(JD/Ca 2+ ) 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 amino trimethylene phosphonic Acid (ATMP), a dispersing scale inhibitor B maleic acid-acrylic acid copolymer (MA/AA), a dispersing scale inhibitor C acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (AA/AMPS) and a dispersing scale inhibitor D sodium polyaspartate (PASP). According to the ratio of the calcium and the alkali in the supplementing water, the contents of different components in the circulating water scale and corrosion inhibitor are adjusted, so that an optimal formula suitable for the water quality is obtained, and the action 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 supplementing water-calcium-alkali ratio is applied to the actual running of the circulating water of the power plant, and the result shows that: the two units (2X 660 MW) 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%, the annual coal-fired cost is saved by about 300 ten thousand yuan in the power plant, and the water yield of unit generated energy is reduced by about 0.26m 3 The water consumption is reduced by about 83 ten thousand tons per year, wherein the water intake of the surface water is reduced by about 130 ten thousand tons, the recycled water of the town is increased by about 47 ten thousand tons, and the method is direct and economicThe benefit is about 230 ten thousand yuan/year, and the additional economic benefit is 210 ten thousand yuan/year.
Drawings
FIG. 1, limiting carbonate hardness of organophosphine scale inhibitor monomers at different concentrations;
FIGS. 2, 9 scale inhibition ratios of the dispersed scale inhibitor monomers at different concentrations;
FIGS. 3 and 6 scale inhibition ratios of the dispersion type scale inhibitor monomers at different concentrations;
FIG. 4, component A vs. JD/Ca 2+ Is a change curve of (2);
FIG. 5, component B vs. JD/Ca 2+ Is a change curve of (2);
FIG. 6, component C with JD/Ca 2+ Is a change curve of (2);
FIG. 7, component D with JD/Ca 2+ Is a change curve of (2);
FIG. 8 shows the variation trend of the limit concentration ratio of supplementing water of a certain power plant along with the concentration of the agent;
FIG. 9, a mixed water dynamic simulation test fouling thermal resistance change trend;
FIG. 10, JD (mmol/L) and JD+Ca 2+ (mg/L) versus run time.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples.
EXAMPLE 1 screening of Scale inhibitor monomers
The information of the scale inhibitor used in the invention is shown in Table 1.
TABLE 1 scale inhibitor information
| Sequence number | Name of the name | Abbreviations (abbreviations) | Morphology of the product | |
|
| 1 | Amino trimethylene phosphonic acid | ATMP | Liquid | 50％ | |
| 2 | Hydroxyethylidene diphosphate | HEDP | Liquid | 50％ | |
| 3 | Ethylenediamine tetramethylene phosphonic acid | EDTMP | Liquid | 18-20％ | |
| 4 | Polyaspartic acid sodium salt | PASP | Liquid | 40％ | |
| 5 | Polyepoxysuccinic acid | PESA | Liquid | 40％ | |
| 6 | Hydrolyzed polymaleic anhydride | HPMA | Liquid | 48％ | |
| 7 | Maleic acid-acrylic acid copolymer | MA/AA | Liquid | 48％ | |
| 8 | Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer | AA/ | Liquid | 30％ | |
| 9 | Iminodisuccinic acid tetrasodium salt | IDS | Liquid | 33-35％ | |
| 10 | Polyacrylic acid | PAA | Liquid | 30％ | |
| 11 | Water-soluble chitosan | / | Solid body | 100％ | |
| 12 | D-gluconic acid sodium salt | / | Solid body | 99％ |
The organic phosphine scale inhibitor monomer is selected from: the scale inhibition performance test of the scale inhibitor monomer is carried out by adopting an extreme carbonate method, wherein the evaluation index is the extreme carbonate hardness, and the test process is referred to HG/T4541-2013 ' determination of the scale inhibition performance of water treatment agent ' extreme carbonate method '. The ultimate carbonate hardness of the organic phosphine scale inhibitor monomer at different concentrations was measured, and the test results are shown in FIG. 1. As can be seen from FIG. 1, the scale inhibition effect of ATMP is significantly better than HEDP and EDTMP.
And (3) selecting a dispersion type scale inhibitor monomer: sodium Polyaspartate (PASP), polyepoxysuccinic acid (PESA), hydrolyzed polymaleic anhydride (HPMA), maleic acid-acrylic acid copolymer (MA/AA), acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (AA/AMPS), tetra sodium Iminodisuccinate (IDS), polyacrylic acid (PAA), water-soluble chitosan and sodium D-gluconate are subjected to scale inhibition performance test of a scale inhibitor monomer by adopting a calcium carbonate deposition method, wherein the evaluation index is a scale inhibition rate, and the test process refers to GB/T16632-2019 'method for measuring calcium carbonate deposition method of scale inhibition performance of a water treatment agent'. The scale inhibition rate of the dispersed scale inhibitor monomer at different concentrations is measured, and the test result is shown in figure 2.
As can be seen from fig. 2, the scale inhibition rate of the dispersion type scale inhibitor monomer generally increases with increasing concentration. 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 were plotted individually as shown in figure 3.
As is clear from fig. 3, the dispersed scale inhibitor monomer PASP has a higher scale inhibition rate at a low dose. The scale inhibition rate of the dispersed scale inhibitor monomer PESA is obviously improved at a higher dosage, but the dispersed scale inhibitor monomer PESA tends to be stable after reaching a certain value. When the concentration of the scale inhibitor is more than 8mg/L, the scale inhibition rate is obviously slow to increase, the scale inhibition rate is 55-70%, and the difference is small.
According to the screening experimental result of the scale inhibitor monomer, and combining certain structural similarity of the scale inhibitors, screening out an organic phosphine scale inhibitor monomer ATMP, a dispersed scale inhibitor monomer MA/AA, a dispersed scale inhibitor monomer AA/AMPS and a dispersed scale inhibitor monomer PASP, and carrying out a compound experiment.
EXAMPLE 2 screening of scale inhibitor formulations
A, B, C, D is respectively represented by an organic phosphine scale inhibitor monomer ATMP, a dispersed scale inhibitor monomer MA/AA, a dispersed scale inhibitor monomer AA/AMPS and a dispersed scale inhibitor monomer PASP, and the scheme is as follows:
(1) The boundaries of the individual scale inhibitor ratios (the blend components, i.e., the ratio of the individual scale inhibitor to the total amount of scale inhibitor) are determined as shown in table 2.
TABLE 2 ratio ranges for the respective scale inhibitors
(2) Mixing uniformity tests using simplex gravity center design are shown in table 3.
TABLE 3 test design sheet
| Numbering device | 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 a ratio of 1/3 of the total amount of the single scale inhibitor to the total amount of the scale inhibitor, as in the following table.
(3) According to the proportion of each component in the test design table, referring to HG/T4541-2013 'determination of scale inhibition Performance of Water treatment agent limit carbonate method', scale inhibition performance test of limit carbonate method is carried out, the test water is shown in the table 4, and respectively represents negative hard water (alkalinity is greater than hardness), temporary hard water (alkalinity is equal to hardness) and permanent hard water (alkalinity is less than hardness) with different calcium-alkali ratios (ratio of alkalinity to calcium ion concentration), wherein alkalinity (JD) represents the total amount of all substances capable of undergoing neutralization reaction with strong acid in water, namely NaHCO in the table 4 below 3 Is a concentration of (2); hardness indicates Ca in water 2+ 、Mg 2+ The ion content, caCl in Table 4 below 2 Is a concentration of (3).
Table 4 test water
Wherein JD/Ca 2+ The representation is: naHCO (NaHCO) 3 (mmol/L) and CaCl 2 (mmol/L) ratio
(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 in the form:
K lim ＝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
using a planning solution tool, Δk is found when a=0.25, b=0.27, c=0.24, d=0.24 lim Obtain the maximum value and calculate the value delta K lim (max) was 2.50.
According to DeltaK lim When the maximum value is obtained, the component content of A, B, C, D is calculated to obtain a verification value delta K lim 2.47.
Table 6 test results of test water 2
The regression equation is in the form:
K lim ＝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
using a planning solution tool, Δk is found when a=0.28, b=0.38, c=0.20, d=0.14 lim Obtain the maximum value and calculate the value delta K lim (max) was 2.69.
According to DeltaK lim When the maximum value is obtained, the component content of A, B, C, D is calculated to obtain a verification value delta K lim 2.68.
TABLE 7 test results for test Water 3
The regression equation is in the form:
K lim ＝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
using a planning solution tool, Δk is found when a=0.32, b=0.39, c=0.19, d=0.10 lim Obtain the maximum value and calculate the value delta K lim (max) was 2.88.
According to DeltaK lim When the maximum value is obtained, the component content of A, B, C, D is calculated to obtain a verification value delta K lim 2.85.
Table 8 test results for test water 4
The regression equation is in the form:
K lim ＝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
using a planning solution tool, Δk is found when a=0.39, b=0.36, c=0.14, d=0.11 lim Obtain the maximum value and calculate the value delta K lim (max) was 3.17.
According to DeltaK lim When the maximum value is obtained, the component content of A, B, C, D is calculated to obtain a verification value delta K lim 3.18.
Table 9 test results of test water 5
The regression equation is in the form:
K lim ＝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
using a planning solution tool, Δk is found when a=0.46, b=0.34, c=0.10, d=0.10 lim Obtain the maximum value and calculate the value delta K lim (max) was 3.53.
According to DeltaK lim When the maximum value is obtained, the component content of A, B, C, D is calculated to obtain a verification value delta K lim 3.50.
Table 10 test results of test water 6
The regression equation is in the form:
K lim ＝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 planning solution tool, Δk is found when a=0.58, b=0.25, c=0.09, d=0.08 lim Obtain the maximum value and the calculated value delta K lim (max) was 4.07.
According to DeltaK lim When the maximum value is obtained, the component content of A, B, C, D is calculated to obtain a verification value delta K lim 4.09.
Table 11 test results of test water 7
The regression equation is in the form:
K lim ＝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
using a planning solution tool, Δk is found when a=0.65, b=0.22, c=0.06, d=0.07 lim Obtain the maximum value and calculate the value delta K lim (max) was 4.80.
According to DeltaK lim When the maximum value is obtained, the component content of A, B, C, D is calculated to obtain a verification value delta K lim 4.77.
(5) Ratio of calcium to alkali (JD/Ca) 2+ ) Relationship with the component content of A, B, C, D
According to the test results of the test waters 1 to 7, ΔK was obtained lim A, B, C, D, the ratio of calcium to alkali (JD/Ca) 2+ ) The relation between the component content and A, B, C, D is shown in Table 12.
TABLE 12 JD/Ca 2+ With A,B. C, D relation of component contents
| Numbering device | JD/Ca 2+ | 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 |
From Table 12, it is found that the ratio of component A to calcium base (JD/Ca 2+ ) See fig. 4.
The regression equation is in the form of: a=0.128+0.264 (JD/Ca 2+ )-0.032(JD/Ca 2+ ) 2
The examination of the model is shown in Table 13.
Table 13 model summary
Wherein, the meaning of R is a correlation coefficient, and the correlation degree of the independent variable and the dependent variable fluctuation is directional and large; r is R 2 The meaning of (1) is a determining coefficient, and the degree to which the reaction regression equation can interpret the sum of squares of the dispersion and the sum of squares of the total dispersion is equal to the square of the correlation coefficient R; adjusting R 2 To overestimate R square to account for increasing the argument, an adjustment to R square is required. The larger the difference between the adjusted R square and R square, the worse the fit of the model.
Component B follows the ratio of calcium to alkali (JD/Ca) 2+ ) See fig. 5.
The regression equation is in the form of:
B＝0.702-0.284(JD/Ca 2+ )+0.043(JD/Ca 2+ ) 2 -0.025/(JD/Ca 2+ )-0.05/(JD/Ca 2+ ) 2
the examination of the model is shown in Table 14.
Table 14 model summary
Component C follows the ratio of calcium to alkali (JD/Ca) 2+ ) See fig. 6.
The regression equation is in the form of: c=0.337 to 0.257 (JD/Ca 2+ )+0.09(JD/Ca 2+ ) 2 -0.011(JD/Ca 2+ ) 3
The examination of the model is shown in Table 15.
Table 15 model summary
Component D follows the ratio of calcium to alkali (JD/Ca) 2+ ) See fig. 7.
The regression equation is in the form of:
D＝0.483-0.168(JD/Ca 2+ )+0.022(JD/Ca 2+ ) 2 -0.35/(JD/Ca 2+ )+0.121/(JD/Ca 2+ ) 2
the examination of the model is shown in Table 16.
Table 16 model summary
Example 3 method for adjusting scale inhibitor formulation
And adjusting the formula of the circulating water scale and corrosion inhibitor based on the ratio of the supplementing water to the calcium and the alkali. The water quality analysis of the supplementing water in the water supplementing surface water and the urban water in a certain power plant is shown in a table 17 because the water inflow amount of the urban water is not fixed, so that the daily ratio of the water supplementing surface water to the urban water is greatly changed.
Table 17 analysis of make-up water quality in a power plant
| Detecting items | Surface water | Reclaimed water treatment system effluent |
| Turbidity (NTU) | 0.97 | 1.42 |
| Conductivity (mu S/cm) | 698 | 1121 |
| pH | 8.0 | 8.1 |
| Phenolphthalein alkalinity (mmol/L) | 0 | 0 |
| Whole alkalinity (mmol/L) | 2.76 | 2.15 |
| Ca 2+ (as CaCO) 3 Meter) (mg/L) | 98 | 350 |
| Total hardness (as CaCO) 3 Meter) (mg/L) | 202 | 400 |
| COD (in O) 2 Meter) (mg/L) | 13 | 28.8 |
| Cl - (mg/L) | 61.4 | 86.7 |
| SO 4 2- (mg/L) | 117 | 180.1 |
According to the water supplementing requirement of the circulating water of the power plant, the surface water and the water discharged from the reclaimed water treatment system are mixed in a 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 quality index of mixed water before concentration
As can be seen from Table 18, as the water ratio of the surface water and the reclaimed water treatment system was changed, the mixed water was gradually changed from negative hard water to permanent hard water, and the ratio of calcium to alkali (JD/Ca 2+ ) The component content of A, B, C, D in the scale inhibitor formula is adjusted according to the component content relation of A, B, C, D.
Mixing water for # 1:
JD/Ca 2+ =2.82, and the component A, B, C, D content of the scale inhibitor was determined according to the test results of example 2. Namely: a=0.128+0.264 (JD/Ca 2+ )-0.032(JD/Ca 2+ ) 2 ，A＝0.62；
B＝0.702-0.284(JD/Ca 2+ )+0.043(JD/Ca 2+ ) 2 -0.025/(JD/Ca 2+ )-0.05/(JD/Ca 2+ ) 2 ，B＝0.23；
C＝0.337-0.257(JD/Ca 2+ )+0.09(JD/Ca 2+ ) 2 -0.011(JD/Ca 2+ ) 3 ，C＝0.08；
D＝0.483-0.168(JD/Ca 2+ )+0.022(JD/Ca 2+ ) 2 -0.35/(JD/Ca 2+ )+0.121/(JD/Ca 2+ ) 2 ，D＝0.08。
For #2 mixed water:
JD/Ca 2+ =1.62, and the component A, B, C, D content of the scale inhibitor was determined according to the test results of example 2. Namely: a=0.128+0.264 (JD/Ca 2+ )-0.032(JD/Ca 2+ ) 2 ，A＝0.47；
B＝0.702-0.284(JD/Ca 2+ )+0.043(JD/Ca 2+ ) 2 -0.025/(JD/Ca 2+ )-0.05/(JD/Ca 2+ ) 2 ，B＝0.32；
C＝0.337-0.257(JD/Ca 2+ )+0.09(JD/Ca 2+ ) 2 -0.011(JD/Ca 2+ ) 3 ，C＝0.11；
D＝0.483-0.168(JD/Ca 2+ )+0.022(JD/Ca 2+ ) 2 -0.35/(JD/Ca 2+ )+0.121/(JD/Ca 2+ ) 2 ，D＝0.10。
Mixing water for # 3:
JD/Ca 2+ =1.10, and the component A, B, C, D content of the scale inhibitor was determined according to the test results of example 2. Namely: a=0.128+0.264 (JD/Ca 2+ )-0.032(JD/Ca 2+ ) 2 ，A＝0.38；
B＝0.702-0.284(JD/Ca 2+ )+0.043(JD/Ca 2+ ) 2 -0.025/(JD/Ca 2+ )-0.05/(JD/Ca 2+ ) 2 ，B＝0.38；
C＝0.337-0.257(JD/Ca 2+ )+0.09(JD/Ca 2+ ) 2 -0.011(JD/Ca 2+ ) 3 ，C＝0.15；
D＝0.483-0.168(JD/Ca 2+ )+0.022(JD/Ca 2+ ) 2 -0.35/(JD/Ca 2+ )+0.121/(JD/Ca 2+ ) 2 ，D＝0.11。
Mixing water for # 4:
JD/Ca 2+ =0.80, and the component A, B, C, D content in the scale inhibitor was determined according to the test results of example 2. Namely: a=0.128+0.264 (JD/Ca 2+ )-0.032(JD/Ca 2+ ) 2 ，A＝0.32；
B＝0.702-0.284(JD/Ca 2+ )+0.043(JD/Ca 2+ ) 2 -0.025/(JD/Ca 2+ )-0.05/(JD/Ca 2+ ) 2 ，B＝0.39；
C＝0.337-0.257(JD/Ca 2+ )+0.09(JD/Ca 2+ ) 2 -0.011(JD/Ca 2+ ) 3 ，C＝0.18；
D＝0.483-0.168(JD/Ca 2+ )+0.022(JD/Ca 2+ ) 2 -0.35/(JD/Ca 2+ )+0.121/(JD/Ca 2+ ) 2 ，D＝0.11。
Mixing water for # 5:
JD/Ca 2+ =0.61, and the component A, B, C, D content of the scale inhibitor was determined according to the test results of example 2. Namely:
A＝0.128+0.264(JD/Ca 2+ )-0.032(JD/Ca 2+ ) 2 ，A＝0.28；
B＝0.702-0.284(JD/Ca 2+ )+0.043(JD/Ca 2+ ) 2 -0.025/(JD/Ca 2+ )-0.05/(JD/Ca 2+ ) 2 ，B＝0.37；
C＝0.337-0.257(JD/Ca 2+ )+0.09(JD/Ca 2+ ) 2 -0.011(JD/Ca 2+ ) 3 ，C＝0.21；
D＝0.483-0.168(JD/Ca 2+ )+0.022(JD/Ca 2+ ) 2 -0.35/(JD/Ca 2+ )+0.121/(JD/Ca 2+ ) 2 ，D＝0.14。
application example 1 determination of scale and corrosion inhibitor formulation according to the calcium-alkali ratio of make-up water
The water quality index of the make-up water of a certain power plant is shown in table 19.
Table 19 Water quality index of make-up water for certain power plant
| Project | Numerical value | Project | Numerical value |
| pH | 7.92 | HCO 3 - (mmol/L) | 3.82 |
| Conductivity (25 ℃ C.) (μS/cm) | 1876 | Phenolphthalein alkalinity (mmol/L) | 0.0 |
| Cl -1 (mg/L) | 234.0 | Total basicity (mmol/L) | 3.82 |
| SO 4 2- (mg/L) | 278.0 | 1/2 Total hardness (mmol/L) | 5.22 |
| CO 3 2- (mg/L) | 0.0 | 1/2 temporary hardness (mmol/L) | 3.82 |
| Ca 2+ (mg/L) | 55.2 | 1/2 permanent hardness (mmol/L) | 0.0 |
| Mg 2+ (mg/L) | 29.5 | SiO 2 mg/L (all silicon) | / |
JD/Ca 2+ =2.77, according to the calcium-to-alkali ratio (JD/Ca 2+ ) And (5) determining the content of the component A, B, C, D in the scale inhibitor respectively according to the component content relation curve of A, B, C, D. Namely:
A＝0.128+0.264(JD/Ca 2+ )-0.032(JD/Ca 2+ ) 2 ，A＝0.61；
B＝0.702-0.284(JD/Ca 2+ )+0.043(JD/Ca 2+ ) 2 -0.025/(JD/Ca 2+ )-0.05/(JD/Ca 2+ ) 2 ，B＝0.23；
C＝0.337-0.257(JD/Ca 2+ )+0.09(JD/Ca 2+ ) 2 -0.011(JD/Ca 2+ ) 3 ，C＝0.07；
D＝0.483-0.168(JD/Ca 2+ )+0.022(JD/Ca 2+ ) 2 -0.35/(JD/Ca 2+ )+0.121/(JD/Ca 2+ ) 2 ，D＝0.09。
the scale and corrosion inhibitor is prepared according to the proportion of the components, the scale and corrosion inhibitor is tested in 2020 by referring to HG/T4541-2013 'determination of the scale inhibition performance of water treatment agent' limit carbonate method ', and the control value of calcium hardness and alkalinity concentration in circulating cooling water is CaCO according to GB/T50050-2017' industrial circulating cooling water treatment design Specification 3 Counting; wherein the calcium hardness and alkalinity in the water quality analysis table of the measurement item are generally in mmol/L, and the alkalinity is 1 mmol/L=50 mg/L (in CaCO) 3 Calculated as CaCO), calcium hardness 1 mmol/L=100 mg/L 3 Meter). The test results are shown in Table 20, table 21, table 22, table 23, table 24, table 25 and FIG. 8, respectively.
TABLE 20 supplemental water static limit carbonate blank for certain Power plant
Wherein K is JD K is the ratio of the alkalinity value in the water to the alkalinity value in the raw water after the raw water is concentrated CL -is the ratio of the concentration value of chloride ions in the water to the concentration value of chloride ions in the raw water after the concentration of the raw water, delta A is K CL - And K is equal to JD When delta A is more than or equal to 0.2, the scale formation of the circulating water is indicated. The table below is the same.
TABLE 21 static limit carbonate test for make-up water for certain plant (dosage 8 mg/L)
TABLE 22 static limit carbonate test for make-up water for certain plant (dosage 10 mg/L)
TABLE 23 static limit carbonate test for make-up water for certain plant (dosage 12 mg/L)
TABLE 24 static limit carbonate test for make-up water for certain plant (dosage 14 mg/L)
Table 25 make-up water static limit carbonate test for certain plant (dosing amount 16 mg/L)
As shown by test results, the concentration of the scale and corrosion inhibitor is lower than 12mg/L, and the concentration of the static limit carbonate of the water sample is increased along with the concentration of the medicament (when delta A is more than or equal to 0.2, K Cl- The limit carbonate concentration ratio) is obviously increased, the static limit carbonate concentration ratio of the water sample is hardly increased along with the continuous increase of the concentration of the chemical agent after the concentration of the scale and corrosion inhibitor is more than 12mg/L, so that the 12mg/L of the scale and corrosion inhibitor in the supplementing water is the optimal concentration, the concentration ratio of the water sample is 3.11, the limit carbonate hardness reaches 12mmol/L, the hardness of the carbonate is stable in comparison with the common scale and corrosion inhibitor, and the scale inhibition performance of the compounded chemical agent is excellent and is improved by more than 30 percent compared with the scale inhibition effect of the common chemical agent.
Application example 2 application of scale inhibitor formula adjustment method
Reference HG/T2160-2008 "method for dynamic simulation test of Cooling Water", and dynamic simulation test is performed in combination with actual running conditions of circulating Water of Power plantThe scale inhibitor formulation adjustment method (component content of A, B, C, D in the scale inhibitor formulation corresponding to the mixed water #1- #5 of example 3) was evaluated. The results of the dynamic simulation test of the mixed water are shown in Table 26. Wherein, full basicity: 1 mmol=50 mg/L (as CaCO) 3 Calculated by the weight of CaCO), for example, the total alkalinity is 2.76mmol/L and the calcium hardness is 98mg/L 3 Calculated as CaCO), then calcium hardness + total alkalinity 3 Meter) = (2.76×50+98) mg/l=236 mg/L (as CaCO) 3 Meter).
Table 26 results of mixed water dynamic simulation test
The thermal resistance change trend of the dirt in the mixed water dynamic simulation test is shown in figure 9. According to the results of dynamic simulation tests, under the condition that the concentration of the scale and corrosion inhibitor added into the mixed water is 8mg/L, when the circulating water supplementing water is changed into the mixed water of #1, #5, #3, #2 and #4 in sequence, the thermal resistance of the dirt grows slowly, and after the mixed water runs for 16 days, the thermal resistance of the dirt is stabilized at about 1.40, and at the moment, the deposition speed and the stripping speed of the dirt are approximately equal. Meets the heat resistance value of dirt on the water side of the heat transfer surface of equipment in GB/T50050-2017 industrial circulating cooling water treatment design Specification not more than 3.44 multiplied by 10 -4 m 2 K/W requirements, which indicate excellent compatibility of the compound medicament under different water qualities.
Alkalinity (mmol/L) of circulating water, calcium hardness and total alkalinity (CaCO) 3 Meter) over run time is shown in fig. 10.
Circulating water supplementWhen the water filling is #1 mixed water, the calcium hardness and the total alkalinity (CaCO) of the circulating water are adopted 3 Calculated by the weight of the total alkalinity should be controlled to 962-990 mg/L and the total alkalinity should be controlled to be below 11.35 mmol/L.
When the circulating water supplementing water is #5 mixed water, the calcium hardness and the total alkalinity (CaCO) of the circulating water are adopted 3 Meter) is controlled to 1715-1750 mg/L and the total alkalinity is controlled to be below 8.25 mmol/L.
When the circulating water supplementing water is #3 mixed water, the calcium hardness and the total alkalinity (CaCO) of the circulating water are adopted 3 Meter) is controlled to 1320-1350 mg/L and the total alkalinity is controlled to be below 9.35 mmol/L.
When the circulating water supplementing water is #2 mixed water, the calcium hardness and the total alkalinity (CaCO) of the circulating water are adopted 3 Meter) should be controlled to 1130-1170 mg/L and the total alkalinity to below 10.26 mmol/L.
When the circulating water supplementing water is #4 mixed water, the calcium hardness and the total alkalinity (CaCO) of the circulating water are adopted 3 Meter) is controlled to be 1490-1540 mg/L and the total alkalinity is controlled to be below 8.69 mmol/L.
Compared with the common scale and corrosion inhibitor, the carbonate with the hardness of 7-8 mmol/L can be stabilized, and the compounded medicament has excellent scale inhibition performance. In addition, when the make-up water is switched to the mixed water with different proportions, the control index of the circulating water is correspondingly changed, so that the concentration multiple of the circulating water is improved to the greatest extent, and the scaling of a condenser pipe is effectively avoided.
The scale inhibitor formula adjustment method based on the water-calcium-alkali supplementing ratio is successfully applied to multiple household appliances, and the result shows that: the two units (2X 660 MW) 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%, the annual coal-fired cost is saved by about 300 ten thousand yuan in the power plant, and the water yield of unit generated energy is reduced by about 0.26m 3 And (MW.h), 83 ten thousand tons of water can be saved each year, wherein the water intake of surface water is reduced by about 130 ten thousand tons, the recycled amount of town reclaimed water is increased by about 47 ten thousand tons, the direct economic benefit is about 230 ten thousand yuan/year, and the additional economic benefit is 210 ten thousand yuan/year.
Claims (2)
1. A method for adjusting a circulating water scale and corrosion inhibitor formula based on the ratio of calcium and alkali in supplementing water is characterized in that the ratio of calcium and alkali is alkalinity to calcium ionsMolar concentration ratio of the subunits, JD/Ca 2+ A representation; JD/Ca 2+ The content relation of the components with A, B, C, D is as follows:
A＝0.128+0.264(JD/Ca 2+ )-0.032(JD/Ca 2+ ) 2 ；
B＝0.702-0.284(JD/Ca 2+ )+0.043(JD/Ca 2+ ) 2 -0.025/(JD/Ca 2+ )-0.05/(JD/Ca 2+ ) 2 ；
C＝0.337-0.257(JD/Ca 2+ )+0.09(JD/Ca 2+ ) 2 -0.011(JD/Ca 2+ ) 3 ；
D＝0.483-0.168(JD/Ca 2+ )+0.022(JD/Ca 2+ ) 2 -0.35/(JD/Ca 2+ )+0.121/(JD/Ca 2+ ) 2 ；
the A is amino trimethylene phosphonic Acid (ATMP), the B is maleic acid-acrylic acid copolymer (MA/AA), the C is acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (AA/AMPS), and the D is sodium polyaspartate (PASP);
the circulating water scale and corrosion inhibitor comprises the following components in percentage by weight: organic phosphine scale inhibitor A:0 to 1, a dispersion scale inhibitor B:0 to 1, a dispersion scale inhibitor C:0 to 1, a dispersion scale inhibitor D:0 to 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. Use of the method according to claim 1 for regulating a circulating water system.
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