CN112299575B - Composite phosphorus-free corrosion and scale inhibitor applied to dry quenching waste heat boiler and preparation method thereof - Google Patents
Composite phosphorus-free corrosion and scale inhibitor applied to dry quenching waste heat boiler and preparation method thereof Download PDFInfo
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- CN112299575B CN112299575B CN202011091263.XA CN202011091263A CN112299575B CN 112299575 B CN112299575 B CN 112299575B CN 202011091263 A CN202011091263 A CN 202011091263A CN 112299575 B CN112299575 B CN 112299575B
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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
- C02F5/12—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 nitrogen
- C02F5/125—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 nitrogen combined with inorganic substances
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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
- 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
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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
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
A composite phosphorus-free corrosion and scale inhibitor applied to a coke dry quenching waste heat boiler and a preparation method thereof are disclosed, wherein the scale inhibitor comprises the following components in parts by weight: 10-40 parts of hydroxypropyl trimethyl ammonium chloride chitosan, 20-50 parts of sodium gluconate, 10-25 parts of N-isopropyl hydroxylamine, 10-30 parts of polyaspartic acid, 5-20 parts of glucoside, 5-20 parts of sodium hydroxide and 20-40 parts of ultrapure water. The agent is green and environment-friendly, effectively reduces the salt content increase of a boiler, avoids the influence of excessive use of the agent on the boiler, ensures that the conductivity of water rises by less than 20 mu s/cm after the agent is used, obviously reduces the times of boiler boiling, reduces the times of chemical cleaning, does not contain phosphorus, is green and environment-friendly, is easy to biodegrade after being discharged, does not produce secondary pollution, has efficient corrosion inhibition, scale inhibition, oxygen removal and easy degradation, and is suitable for being used in a dry quenching waste heat boiler.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a composite phosphorus-free corrosion and scale inhibitor applied to a coke dry quenching waste heat boiler and a preparation method thereof.
Background
The dry quenching waste heat boiler is generally a secondary high-pressure boiler or a high-pressure boiler, and is mainly equipment for recovering waste heat in coke dry quenching to generate steam, the requirement on water quality of the boiler is high, ultrapure water is required to be used as make-up water, a composite scale inhibitor mainly comprising phosphate is generally added in order to inhibit corrosion and scaling phenomena in the operation of the boiler, but phosphate scale is inevitably generated along with the continuous operation of the equipment, the corrosion of the scale easily causes the explosion of a boiler tube in the boiler after the accumulation of the scale in the future, combustible components in circulating water are rapidly increased, the explosion of the whole closed circulating gas is caused, and serious safety accidents are caused.
Although the composite corrosion and scale inhibitor mainly adopting phosphate is economical and practical, the generated defects can not be ignored, the phenomenon that phosphate is hidden easily occurs when a large amount of phosphate is used, the reason is that partial phosphate is separated out and scales, hidden danger is buried in a boiler, equipment loss and medicament waste can be caused by regular boiler boiling, the production cost is increased indirectly, and the phosphorus-based corrosion and scale inhibitor adopted at present has high phosphorus content in wastewater discharged, and environmental pollution is easily caused. In view of the above problems, it is not appropriate to use a composite corrosion and scale inhibitor mainly composed of phosphate for a long time.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a phosphorus-free corrosion and scale inhibitor which does not contain phosphorus and can maintain the corrosion and scale inhibition effect for a long time, the agent is green and environment-friendly, the salt content increase of a boiler can be effectively reduced, the influence of excessive use of the agent on the boiler is avoided, the conductivity of water rises by less than 20 mu s/cm after the agent is used, the boiler boiling times are obviously reduced, the chemical cleaning times are effectively reduced, the agent does not contain phosphorus, is green and environment-friendly, is easy to biodegrade after being discharged, does not generate secondary pollution, has high-efficiency corrosion inhibition, scale inhibition, deoxidation and degradability, and is suitable for being used in a dry coke quenching waste heat boiler.
In order to achieve the purpose, the invention adopts the following technical scheme:
the composite phosphorus-free corrosion and scale inhibitor applied to the coke dry quenching waste heat boiler comprises the following components in parts by weight: 10-40 parts of hydroxypropyl trimethyl ammonium chloride chitosan, 20-50 parts of sodium gluconate, 10-25 parts of N-isopropyl hydroxylamine, 10-30 parts of polyaspartic acid, 5-20 parts of glucoside, 5-20 parts of sodium hydroxide and 20-40 parts of ultrapure water.
The scale inhibitor comprises the following components in parts by weight: 20-30 parts of hydroxypropyl trimethyl ammonium chloride chitosan, 25-40 parts of sodium gluconate, 13-20 parts of N-isopropyl hydroxylamine, 15-25 parts of polyaspartic acid, 7-15 parts of glucoside, 8-17 parts of sodium hydroxide and 20-40 parts of ultrapure water.
The sodium gluconate is a polyhydroxy acid type corrosion and scale inhibitor, is non-toxic and environment-friendly, has double functions of corrosion and scale inhibition, the corrosion inhibition effect of the sodium gluconate is increased along with the rise of temperature, and the sodium gluconate has excellent coordination capacity to ions such as iron, calcium, copper and the like in aqueous solution and has good descaling effect on salts formed by the ions. The sodium gluconate is matched with the polyaspartic acid and the hydroxypropyl trimethyl ammonium chloride chitosan to play a good role in coordination and synergism.
The pH value of the polyaspartic acid is 9.5, the polyaspartic acid is an alkaline medicament, the polyaspartic acid is a novel green water treatment agent, has the characteristics of no phosphorus, no toxicity, no pollution and complete biodegradation, is suitable for various industrial circulating cooling water and boiler water, particularly has strong chelating capacity for metal ions in the boiler water, has various effects of corrosion inhibition, scale inhibition and dispersion, and can play a comprehensive protection role when used in a dry quenching waste heat boiler. The polyaspartic acid can be used in combination with various water treatment agents to play a role in coordination and synergism.
N-isopropyl hydroxylamine (IPHA), belonging to alkaline medicament, non-toxic, is a good deoxidant for removing dissolved oxygen, has better volatility, and has a gas-liquid ratio of 1.
The glucoside (APG) is a green surfactant with comprehensive performance, has strong compatibility, high surface activity, good ecological safety and intermiscibility, can disperse impurities in a boiler and impurities flocculated by the hydroxypropyl trimethyl ammonium chloride chitosan in water, and effectively avoids deposition and scaling.
The sodium hydroxide is mainly used as a pH regulator, and the pH value of water is required to be over 9.0 when the dry quenching waste heat boiler operates, so the sodium hydroxide has the effect of regulating the pH value of a medicament and the pH value of boiler water.
The ultrapure water is the effluent of EDI high-purity water equipment, and mainly has the function of eliminating system pollution caused by water quality with more impurities as much as possible, so that the operation of the dry quenching waste heat boiler is more guaranteed.
The preparation method of the composite phosphorus-free corrosion and scale inhibitor applied to the coke dry quenching waste heat boiler comprises the following steps:
injecting ultrapure water into a pressure-bearing reaction kettle at room temperature, heating to 40-60 ℃, then carrying out vacuum-pumping treatment, exhausting air by adopting a direct-connected liquid ring vacuum pump, adding hydroxypropyl trimethyl ammonium chloride chitosan, sodium gluconate and N-isopropyl hydroxylamine through a reserved closed dosing port (vacuumized), mixing and stirring for no less than 30min, adding polyaspartic acid and glucoside after all the materials are dissolved, continuously stirring for no less than 1h, keeping the heating temperature at 40-60 ℃, finally adding a pH regulator sodium hydroxide, continuously stirring for no less than 30min, and naturally cooling to room temperature.
The ultimate vacuum pressure reaches 0.092-0.098MPa.
The application of the corrosion and scale inhibitor in the coke dry quenching waste heat boiler can control the conductivity rise in water within 20 mu s/cm, relatively less salt phase is brought in by the complexing agent, the influence on the boiler is avoided, the traditional corrosion and scale inhibitor for the phosphate boiler continuously accumulates medicament residues in the boiler along with the advancing of time, more phosphate is accumulated, and the chemical cleaning of the boiler is finally carried out. The hydroxypropyl trimethyl ammonium chloride chitosan, the sodium gluconate, the N-isopropyl hydroxylamine, the polyaspartic acid and the glucoside adopted by the invention have short attenuation period, average attenuation of 50% in one day, mutual compatibility among the components, obvious coordination and synergism, high-efficiency corrosion inhibition, scale inhibition and oxygen removal, and can be suitable for a dry quenching waste heat boiler.
The components of the composite phosphorus-free corrosion and scale inhibitor applied to the coke dry quenching waste heat boiler are all of industrial purity, and in the preparation process, the invention adopts a vacuumizing production method to prevent oxygen in the air from entering the agent in the production process, so that the oxidation attenuation of the deoxidant N-isopropyl hydroxylamine in the preparation process is prevented, the activity of the deoxidant N-isopropyl hydroxylamine is ensured, and the deoxidization and protection performance of the composite agent is improved.
Compared with the prior art, the invention has the beneficial effects that:
1) After the composite phosphorus-free corrosion and scale inhibitor is used, the conductivity of the boiler water rises by less than 20 mu s/cm, the increase of salt in the boiler can be effectively reduced, the influence of excessive use of a medicament on the boiler is avoided, the chemical cleaning times are indirectly reduced, and the cleaning cost is saved.
2) The composite phosphorus-free corrosion and scale inhibitor is phosphorus-free, green and environment-friendly, and after boiler water is discharged, the chemical in the water is easy to biodegrade, and secondary pollution is avoided.
3) The components of the composite phosphorus-free corrosion and scale inhibitor have good cooperativity and compatibility, and the compatibility among medicaments is good, so that the composite phosphorus-free corrosion and scale inhibitor has high-efficiency corrosion inhibition, scale inhibition and oxygen removal.
4) The invention is particularly suitable for being popularized and used in a coke dry quenching waste heat boiler.
5) The complexing agent disclosed by the invention contains N-isopropylhydroxylamine, so that the complexing agent has the characteristic of deoxidization, and can be used in a coke dry quenching waste heat boiler without using the deoxidization agent separately.
Detailed Description
The present invention will be described in detail with reference to examples, but it should be noted that the practice of the present invention is not limited to the following embodiments.
Example 1:
the composite phosphorus-free corrosion and scale inhibitor applied to the coke dry quenching waste heat boiler comprises the following components in percentage by weight: 26 parts of sodium gluconate: 34 parts of N-isopropylhydroxylamine: 18 parts of polyaspartic acid: 18 parts of glucoside: 12 parts, sodium hydroxide: 8 parts of ultrapure water: 30 parts of the raw materials.
The preparation method of the composite scale and corrosion inhibition medicament of the embodiment specifically comprises the following operations:
injecting ultrapure water into a pressure-bearing type reaction kettle at room temperature, heating to 45 ℃, then vacuumizing, discharging air by adopting a direct-connected liquid ring vacuum pump, enabling the ultimate vacuum pressure to reach 0.095MPa, adding hydroxypropyl trimethyl ammonium chloride chitosan, sodium gluconate and N-isopropyl hydroxylamine through a reserved closed medicine adding port device (vacuumized), mixing and stirring for 30min, after all components are dissolved, adding polyaspartic acid and glucoside, continuously stirring for 1h, keeping the heating temperature at 50 ℃, finally adding sodium hydroxide serving as a pH regulator, stirring for 30min, and naturally cooling to room temperature to obtain the product 1#.
Example 2:
the composite phosphorus-free corrosion and scale inhibitor applied to the coke dry quenching waste heat boiler comprises the following components in percentage by weight: 22 parts and sodium gluconate: 38 parts of N-isopropylhydroxylamine: 13 parts of polyaspartic acid: 20 parts of glucoside: 7 parts of sodium hydroxide: 13 parts of ultrapure water: and 25 parts of the total weight.
The preparation method of the composite scale and corrosion inhibition medicament of the embodiment specifically comprises the following operations:
injecting ultrapure water into a pressure-bearing reaction kettle at room temperature, heating to 60 ℃, then vacuumizing, exhausting air by using a direct-connected liquid ring vacuum pump, enabling the limit vacuum pressure to reach 0.097MPa, adding hydroxypropyl trimethyl ammonium chloride chitosan, sodium gluconate and N-isopropyl hydroxylamine through a reserved closed medicine adding port device (vacuumized), mixing and stirring for 30min, after all the materials are dissolved, adding polyaspartic acid and glucoside, continuously stirring for 1h, keeping the heating temperature at 55 ℃, finally adding a pH regulator sodium hydroxide, stirring for 30min, and naturally cooling to room temperature to obtain the product 2#.
Example 3:
the composite phosphorus-free corrosion and scale inhibitor applied to the coke dry quenching waste heat boiler comprises the following components in parts by weight: 30 parts of sodium gluconate: 27 parts of N-isopropylhydroxylamine: 15 parts of polyaspartic acid: 25 parts of glucoside: 15 parts of sodium hydroxide: 15 parts of ultrapure water: 28 parts.
The preparation method of the composite scale and corrosion inhibition medicament of the embodiment specifically comprises the following operations:
injecting ultrapure water into a pressure-bearing reaction kettle at room temperature, heating to 55 ℃, then carrying out vacuum pumping treatment, discharging air by adopting a direct-connected liquid ring vacuum pump, enabling the limit vacuum pressure to reach 0.093MPa, adding hydroxypropyl trimethyl ammonium chloride chitosan, sodium gluconate and N-isopropyl hydroxylamine through a reserved closed medicine adding port device (vacuumized), mixing and stirring for 30min, after all the materials are dissolved, adding polyaspartic acid and glucoside, continuously stirring for 1h, keeping the heating temperature at 55 ℃, finally adding a pH regulator sodium hydroxide, stirring for 30min, and naturally cooling to room temperature to obtain the product 3#.
Experiment 1:
the composite phosphorus-free corrosion and scale inhibitor products 1#, 2#, and 3# of the above examples 1-3 were subjected to simulation experiments under the following limiting water quality conditions, wherein the pH value was 8.52, cond 178 μ s/cm, and the total calcium hardness was 50mg/L (as CaCO) 3 Calculated as CaCO), calcium hardness 20mg/L 3 Meter), cl - 20mg/L and total alkalinity of 65mg/L (as CaCO) 3 Meter). The time is 14 days, ultrapure water is adopted for supplementing water, and a corrosion and scale inhibition performance test is carried out according to a dynamic evaluation method of performance of a boiler water treatment agent (HG/T3924-2007), and the results are shown in Table 1:
table 1 examples 1-3 product performance test results
The results in Table 1 show that the oxygen removal performance, corrosion inhibition rate and scale inhibition rate of products No. 1, no. 2 and No. 3 all meet the corrosion and scale inhibition requirements of industrial boilers, and the electric conductivity after the experiment rises by less than 20 mus/cm, which indicates that the salt brought into the water quality by the medicament is in a controllable range and meets the use requirements of the coke dry quenching waste heat boilers.
Experiment 2:
the composite phosphorus-free corrosion and scale inhibitor products 1#, 2#, and 3# of the above examples 1-3 were subjected to simulation experiments under the following limiting water quality conditions, wherein the pH value was 8.65, cond 217 μ s/cm, and the total calcium hardness was 80mg/L (as CaCO) 3 Calculated as CaCO), calcium hardness of 40mg/L 3 Meter), cl - 40mg/L and total alkalinity of 78mg/L (as CaCO) 3 Meter). The time is 14 days, and the corrosion and scale inhibition performance test is carried out according to dynamic evaluation method of boiler water treatment agent performance (HG/T3924-2007), and the results are shown in Table 2:
table 2 examples 1-3 product performance test results
The results in Table 2 show that the oxygen removal performance, corrosion inhibition rate and scale inhibition rate of products No. 1, no. 2 and No. 3 all meet the corrosion and scale inhibition requirements of an industrial boiler, and the electric conductivity after the experiment rises by less than 20 microseconds per centimeter, which indicates that the salt brought into water by the medicament is in a controllable range and meets the use requirements of a coke dry quenching waste heat boiler.
Experiment 3:
in the simulation experiment, the composite phosphorus-free corrosion and scale inhibitor product 3 has the best effect, the product 3# is selected to be subjected to an online experiment in a coke dry quenching waste heat boiler of a certain steel mill, and the water quality conditions are shown in the following table 3:
table 3: water quality condition for 3# product test
Under the water quality condition in the table 3, the operation time is 1 month, the conductivity in the water is detected every week, the temperature of each part of the boiler is tracked and recorded, and finally the test result is analyzed, so that the boiler operates well, no temperature alarm is given once, the corrosion rate of the carbon steel is 0.0217mm/a, the average dissolved oxygen is 6 mu g/L, the average conductivity in the water of the boiler is 51.4 mu s/cm, the requirement that the conductivity rises to be less than 20 mu s/cm is met, and the using effect in the boiler is good.
Claims (3)
1. The composite phosphorus-free corrosion and scale inhibitor applied to the coke dry quenching waste heat boiler is characterized by comprising the following components in parts by weight: 10-40 parts of hydroxypropyl trimethyl ammonium chloride chitosan, 20-50 parts of sodium gluconate, 10-25 parts of N-isopropyl hydroxylamine, 10-30 parts of polyaspartic acid, 5-20 parts of glucoside, 5-20 parts of sodium hydroxide and 20-40 parts of ultrapure water;
the hydroxypropyl trimethyl ammonium chloride chitosan, the sodium gluconate, the N-isopropyl hydroxylamine, the polyaspartic acid and the glucoside in the components are attenuated by 50 percent in one day on average, and the conductivity of water can be increased and controlled within 20 mu s/cm when the hydroxypropyl trimethyl ammonium chloride chitosan, the sodium gluconate, the N-isopropyl hydroxylamine, the polyaspartic acid and the glucoside are applied to a dry quenching waste heat boiler;
the preparation method of the composite phosphorus-free corrosion and scale inhibitor applied to the coke dry quenching waste heat boiler comprises the following steps:
injecting ultrapure water into a pressure-bearing type reaction kettle, heating to 40-60 ℃, then carrying out vacuum pumping treatment, adding hydroxypropyl trimethyl ammonium chloride chitosan, sodium gluconate and N-isopropyl hydroxylamine through a reserved closed medicine adding port, mixing and stirring, adding polyaspartic acid and glucoside for continuous stirring after all the materials are dissolved, keeping the heating temperature at 40-60 ℃, finally adding a pH regulator sodium hydroxide, continuing stirring, and naturally cooling to room temperature.
2. The composite phosphorus-free corrosion and scale inhibitor applied to the coke dry quenching waste heat boiler of claim 1 is characterized by comprising the following components in parts by weight: 20-30 parts of hydroxypropyl trimethyl ammonium chloride chitosan, 25-40 parts of sodium gluconate, 13-20 parts of N-isopropyl hydroxylamine, 15-25 parts of polyaspartic acid, 7-15 parts of glucoside, 8-17 parts of sodium hydroxide and 20-40 parts of ultrapure water.
3. The composite phosphorus-free corrosion and scale inhibitor applied to the dry quenching waste heat boiler of claim 1, wherein the ultimate vacuum pressure reaches 0.092-0.098MPa.
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| US5152902A (en) * | 1991-03-19 | 1992-10-06 | Donlar Corporation | Polyaspartic acid as a calcium carbonate and a calcium phosphate inhibitor |
| CN105502698B (en) * | 2014-10-14 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of composite scale-inhibiting corrosion inhibitor and its application in circulating water cooling treatment |
| CN106277379A (en) * | 2016-09-30 | 2017-01-04 | 武汉理工大学 | A kind of environment-friendly chitosan compound corrosion inhibiting and descaling agent and preparation method thereof |
| CN108862643A (en) * | 2018-06-28 | 2018-11-23 | 芜湖市棠华建材科技有限公司 | The antisludging agent of boiler recirculated water |
| CN109133392B (en) * | 2018-10-17 | 2021-12-10 | 何云飞 | Green low-phosphorus environment-friendly boiler treatment agent with scale inhibition, descaling, corrosion prevention and oxygen removal functions |
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