CN109293015B - Industrial circulating water treatment agent - Google Patents
Industrial circulating water treatment agent Download PDFInfo
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- CN109293015B CN109293015B CN201811270515.8A CN201811270515A CN109293015B CN 109293015 B CN109293015 B CN 109293015B CN 201811270515 A CN201811270515 A CN 201811270515A CN 109293015 B CN109293015 B CN 109293015B
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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
- C02F5/02—Softening water by precipitation of the hardness
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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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Abstract
The invention belongs to the technical field of sewage treatment, and particularly discloses an industrial circulating water treatment agent which comprises the following raw materials in parts by weight: 0.5-2 parts of surfactant, 20-35 parts of compound corrosion inhibitor, 12-25 parts of scale inhibitor, 1-8 parts of bactericide and 30-60 parts of water; the compound corrosion inhibitor comprises: imidazoline, oxalyl hydrazine compounds, sodium erythorbate and zinc salts. When the circulating water treatment agent disclosed by the invention is used in the water treatment process, good effects of scale inhibition, slow release and sterilization can be obtained, and the harm of phosphorus pollution can not be brought.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to an industrial circulating water treatment agent.
Background
With the continuous development of national economy, water resources become more and more tense, and water conservation becomes an important content of the national policy of environmental protection. Domestic urban industrial water accounts for about 80% of the total urban water, the consumption of industrial circulating cooling water accounts for about 2/3% of the industrial water, the consumption of circulating cooling water in the petroleum and petrochemical industry accounts for a larger proportion and accounts for about 80% -90% of the water consumption of the industrial water, and therefore the consumption of the circulating cooling water is very necessary.
In the daily operation process of the circulating cooling water, salts in the water are concentrated due to continuous evaporation, and the content of dissolved oxygen and bacteria is greatly increased due to the contact of the cooling water and the atmosphere, so that the circulating cooling water has three defects of serious scaling, corrosion and bacterial and algal breeding, the heat exchange rate is greatly reduced, the maintenance is frequent, and the normal production is threatened. The circulating water treatment agent is a chemical agent necessary for the treatment process of industrial water and wastewater in equipment such as a cooling water tower, a cold water machine and the like, and the water can meet certain quality requirements by using the chemical agent so as to be continuously used and achieve the effect of saving water; meanwhile, the system also ensures that equipment such as a cooling water tower, a cold water machine and the like are in the optimal running state, effectively controls microbial flora, inhibits the generation of scale, prevents the corrosion of pipeline equipment, and achieves the purposes of reducing energy consumption and prolonging the service life of the equipment.
Circulating water treatment agents comprise scale inhibition dispersants, corrosion inhibitors, sterilization algicides and the like, and currently, the commonly used scale inhibition dispersants mainly comprise polyphosphates, organic phosphonates, polycarboxylates and natural dispersants; commonly used corrosion inhibitors include inorganic metal-based corrosion inhibitors, inorganic phosphate-based corrosion inhibitors and organic corrosion inhibitors; commonly used bactericides include chlorine agents, quaternary ammonium salt agents, bromine agents, organic nitrogen and sulfur agents and the like.
The currently common circulating water treatment agent contains phosphorus, but with the progress of society and the enhancement of environmental awareness, phosphorus pollution has attracted extensive attention. Phosphorus is not easy to decompose in aqueous solution, and can change the crystal form of calcium carbonate crystals, so that calcium carbonate scales to become irregular crystals which are loosely arranged on the pipe wall. The organic phosphorus is finally decomposed into orthophosphate, which provides a nutrient source for the growth of microorganisms in the sewage and causes environmental pollution.
Disclosure of Invention
The invention aims to provide an industrial circulating water treatment agent to solve the problem of phosphorus pollution caused by the existing circulating water treatment agent.
In order to achieve the purpose, the basic scheme of the invention is as follows: an industrial circulating water treatment agent comprises the following raw materials in parts by weight: 0.5-2 parts of surfactant, 20-35 parts of compound corrosion inhibitor, 12-25 parts of scale inhibitor, 1-8 parts of bactericide and 30-60 parts of water; the compound corrosion inhibitor comprises: modified imidazoline, oxalyl hydrazine compounds, sodium erythorbate and zinc salt.
The beneficial effect of this basic scheme lies in:
1. the raw materials selected by the circulating water treatment agent in the scheme of the invention are free from phosphorus-containing components, so that phosphorus pollution is avoided, and the circulating water treatment agent is green and environment-friendly.
2. The treatment agent has good solubility and stability, is suitable for a circulating water treatment system under severe conditions of high temperature, high hardness and the like, and can be widely applied. The treatment agent can effectively reduce the metal corrosion speed, eliminate oil stains, dissolve old scales and ensure the clean operation of systems and equipment.
3. Sodium isoascorbate contains enol structure, and reacts with oxygen to reduce the content of dissolved oxygen in water, thereby slowing down the oxygen corrosion speed. Meanwhile, sodium erythorbate and oxalyl hydrazine compounds have a synergistic effect, not only can effectively inhibit the catalytic oxidation of metal ions, but also can form a complex with high thermal stability with metals, so that the metal ions lose activity, a compact protective film can be formed on the surface of carbon steel, and the anode process of iron dissolution can be inhibited.
4. The modified imidazoline, the oxalyl hydrazine compounds, the sodium erythorbate and the zinc salt are matched to obtain the compound corrosion inhibitor, and the synergistic cooperation of the agents retards the reaction of the two electrodes, so that the compound corrosion inhibitor can better inhibit the corrosion of metals.
Further, the modified imidazoline is prepared by the following steps:
(1) preparing raw materials: 1.2-2mol of lauric acid, 0.4-1mol of ricinoleic acid, 2-3.2mol of diethylenetriamine, 1.8-2.4mol of thiosemicarbazide and 35-45ml of n-octanol;
(2) uniformly mixing lauric acid, castor oil and diethylenetriamine, adding dimethylbenzene serving as a water carrying agent, stirring, and heating to 140-160 ℃ in the stirring process to dehydrate for 2-3 h; continuously heating to 225-245 ℃ for cyclodehydration, reacting for 1.5-2h, cooling to 110-120 ℃, and removing xylene and unreacted diethylenetriamine through reduced pressure distillation to obtain an intermediate;
(3) heating and stirring the intermediate, dropwise adding anhydrous acetic acid at 48-53 ℃ to enable the pH to be close to 7, reacting for 0.5-1h, and cooling to room temperature to obtain a modified intermediate;
(4) and adding thiosemicarbazide and n-octanol into the modified intermediate for vulcanization treatment, continuously stirring the mixed solution, heating to 160 ℃ for condensation reaction for 3-4h, and then performing reduced pressure distillation at 132 ℃ by using a vacuum pump to obtain the modified imidazoline.
The applicant researches and discovers that lauric acid, ricinoleic acid and diethylenetriamine are selected as main raw materials to synthesize imidazoline, and although the structures and properties of the obtained lauric acid type imidazoline and ricinoleic acid type imidazoline are different, the lauric acid type imidazoline and the ricinoleic acid type imidazoline are complementary to each other, and a dense protective film can be formed on the surface of metal. In the step (3), anhydrous acetic acid is dripped to modify the intermediate, so that the finally obtained modified imidazoline obtains enough hydrophilic groups, the water solubility of the modified imidazoline is greatly improved, and the modified imidazoline can be better applied to circulating water. Through the treatment in the step (3), the water solubility of imidazoline is improved, but the introduction of hydrophilic groups influences the speed and quality of the imidazoline for forming a protective film on the metal surface, so that the corrosion inhibition effect of the imidazoline is influenced. The modified intermediate is subjected to vulcanization treatment, so that the binding capacity of the modified imidazoline and metal is enhanced, a stable adsorption film is favorably formed, and the corrosion inhibition effect of the modified imidazoline is ensured.
Further, the compound corrosion inhibitor comprises the following raw materials in parts by weight: 16-25 parts of modified imidazoline, 5-12 parts of oxalyl hydrazine compounds, 2-7 parts of sodium erythorbate and 4-9 parts of zinc salt. Through a plurality of researches of the applicant, the dosage of the raw materials of the compound corrosion inhibitor is controlled in the range, and the corrosion inhibition effect of the medicament is better on the whole.
Further, the compound corrosion inhibitor also comprises 10-15 parts of gluconate, and the gluconate is D-sodium gluconate or D-potassium gluconate. Gluconate as cathode corrosion inhibitor may be mixed with Fe3+The chelation forms a compact protective film, the reaction of the two electrodes is retarded by using the yin-yang corrosion inhibitor in the medicament at the same time, and the raw materials are mutually synergistic, so that the medicament can better inhibit the corrosion of metal. And the zinc salt is matched with the gluconate, so that the zinc salt can overcome the defect of slow film forming of the gluconate, and the gluconate containing a plurality of hydroxyl groups and carboxyl groups makes up the defect of non-persistent film forming of the zinc salt, so that the formed protective film is more compact and durable.
Further, the feed comprises the following raw materials in parts by mass: 0.8-1.8 parts of surfactant, 26-32 parts of compound corrosion inhibitor, 17-23 parts of scale inhibitor, 4-8 parts of bactericide and 40-50 parts of water; the compound corrosion inhibitor comprises the following raw materials in parts by weight: 24-28 parts of modified imidazoline, 9-12 parts of oxalyl hydrazine compounds, 2-5 parts of sodium erythorbate, 6-9 parts of zinc salt and 10-12 parts of gluconate. Through a plurality of researches of the applicant, the dosage of the raw materials of the medicament is controlled in the range, and the prepared medicament has good corrosion inhibition effect, scale inhibition effect and sterilization effect.
Further, the scale inhibitor comprises the following raw materials in parts by weight: 5-12 parts of polyacrylic acid, 8-15 parts of tannic acid and 8-16 parts of acrylic copolymer. The acrylic copolymer contains-COOH functional group and Ca2+、Mg2+、Fe3+、 Cu2+The plasma has strong chelating ability, not only has dispersing and condensing functions, but also can interfere the normal arrangement of crystal lattices in the crystallization process of inorganic scale, thereby achieving the effects of scale inhibition and scale prevention. The polyacrylic acid has the advantages of low toxicity, low price, solvent-limiting effect and good scale inhibition effect. Tannic acid is a natural scale inhibitor, and is matched with polyacrylic acid and acrylic acid copolymer for use, the average scale inhibition rate on various scales can reach 92%, the scale inhibition rate on calcium carbonate scales is higher than 99.4%, and the scale inhibition effect is obvious. The tannic acid has good oxidation resistance, has a synergistic effect when being matched with sodium erythorbate and oxalyl hydrazine compounds, can effectively slow down the oxygen corrosion speed, and improves the corrosion inhibition effect of the medicament.
Further, the relative molecular mass of the polyacrylic acid is 2000-3000. The applicant finds out through experiments that the relative molecular mass of the polyacrylic acid is controlled to be 2000-3000, and the scale inhibition performance of the scale inhibitor is better.
Further, the bactericide comprises the following raw materials in parts by weight: 5-8 parts of dithiocyano-methane and 6-12 parts of glutaraldehyde. The dithiocyano-methane and the glutaraldehyde are compounded for use, so that the bactericide has more excellent effect.
Further, the surfactant is quaternary ammonium salt surfactant, and is one or more of dodecyl dimethyl benzyl ammonium chloride, polyquaternary ammonium salt and tetradecyl dimethyl benzyl ammonium chloride. The surfactant is added into the medicament, and the surfactant is favorable for forming a corrosion inhibition film with good effect on the surface of the metal. The surfactant in the scheme also has the following beneficial effects that the quaternary ammonium surfactant has broad-spectrum and efficient sterilization and algae removal capability, can effectively control the propagation and slime growth of the bacteria and algae in water, and can better exert the sterilization effect of the medicament by matching with dithiocyano-methane and glutaraldehyde in the bactericide. Meanwhile, the quaternary ammonium salt surfactant also has a certain corrosion inhibition effect, and is used together with a compound corrosion inhibitor, so that the adsorption effect is enhanced, and the broad spectrum of the corrosion inhibitor is greatly improved.
Detailed Description
The following description will explain the selection of raw materials and further describe the present invention in detail by way of specific embodiments, and the comparative example shows only the differences from example 1, and the others are the same as example 1.
The oxalyl hydrazine compounds in the embodiment are synthesized by the following method: reacting 3, 5-di-tert-butyl-4-hydroxyphenyl propionyl chloride with p-hydroxybenzaldehyde and then reacting with oxalyl hydrazine to generate a product;
the zinc salt in this embodiment may be selected from zinc molybdate, zinc sulfate, zinc nitrate, and zinc acetate;
the acrylic copolymer in this embodiment is synthesized by using itaconic acid and acrylic acid as monomers and adopting an aqueous solution radical polymerization reaction.
Example 1
An industrial circulating water treatment agent comprises the following raw materials in parts by weight: 1.2 parts of dodecyl dimethyl benzyl ammonium chloride, 29 parts of compound corrosion inhibitor, 21 parts of scale inhibitor, 5 parts of bactericide and 42 parts of water. The compound corrosion inhibitor comprises the following raw materials in parts by weight: 25 parts of modified imidazoline, 10 parts of oxalyl hydrazine compounds, 5 parts of sodium erythorbate, 7 parts of zinc sulfate and 10 parts of D-sodium gluconate; the scale inhibitor comprises the following raw materials in parts by weight: 9 parts of polyacrylic acid, 12 parts of tannic acid and 16 parts of acrylic copolymer; the bactericide comprises the following raw materials in parts by weight: 7 parts of dithiocyano-methane and 10 parts of glutaraldehyde.
The modified imidazoline in the embodiment is prepared by the following steps:
(1) preparing raw materials: 1.4mol of lauric acid, 0.6mol of ricinoleic acid, 2.4mol of diethylenetriamine, 2mol of thiosemicarbazide and 35ml of n-octanol;
(2) mixing lauric acid, ricinoleic acid and diethylenetriamine uniformly, adding dimethylbenzene serving as a water carrying agent, stirring, and heating to 148 ℃ in the stirring process to perform amide removal for 2.5 hours; continuously heating to 230 ℃ for cyclodehydration, reacting for 1.8h, cooling to 113 ℃, distilling for 0.5h under reduced pressure by using a vacuum pump to remove xylene and unreacted diethylenetriamine to obtain an intermediate;
(3) heating and stirring the intermediate, dropwise adding anhydrous acetic acid at 50 ℃ to enable the pH to be close to 7, reacting for 0.6h, and cooling to room temperature to obtain a modified intermediate;
(4) and adding thiosemicarbazide and n-octanol into the modified intermediate for vulcanization, continuously stirring the mixed solution, heating to 148 ℃ for condensation reaction for 3.5 hours, and then carrying out reduced pressure distillation at 128 ℃ by using a vacuum pump to obtain modified imidazoline.
Example 2
An industrial circulating water treatment agent comprises the following raw materials in parts by weight: 1.5 parts of tetradecyl dimethyl benzyl ammonium chloride, 30 parts of compound corrosion inhibitor, 20 parts of scale inhibitor, 7 parts of bactericide and 45 parts of water. The compound corrosion inhibitor comprises the following raw materials in parts by weight: 24 parts of modified imidazoline, 12 parts of oxalyl hydrazine compounds, 4 parts of sodium erythorbate, 6 parts of zinc sulfate and 12 parts of D-sodium gluconate; the scale inhibitor comprises the following raw materials in parts by weight: 8 parts of polyacrylic acid, 10 parts of tannic acid and 15 parts of acrylic copolymer; the bactericide comprises the following raw materials in parts by weight: 6 parts of dithiocyano-methane and 12 parts of glutaraldehyde.
The modified imidazoline in the embodiment is prepared by the following steps:
(1) preparing raw materials: 1.5mol of lauric acid, 0.8mol of ricinoleic acid, 2.6mol of diethylenetriamine, 2mol of thiosemicarbazide and 32ml of n-octanol;
(2) mixing lauric acid, ricinoleic acid and diethylenetriamine uniformly, adding xylene as a water carrying agent, stirring, and heating to 154 ℃ in the stirring process to perform amide removal for 3 hours; continuously heating to 238 ℃ for cyclodehydration, reacting for 2h, cooling to 115 ℃, distilling for 0.5h under reduced pressure by using a vacuum pump to remove xylene and unreacted diethylenetriamine to obtain an intermediate;
(3) heating and stirring the intermediate, dropwise adding anhydrous acetic acid at 50 ℃ to enable the pH to be close to 7, reacting for 0.6h, and cooling to room temperature to obtain a modified intermediate;
(4) and adding thiosemicarbazide and n-octanol into the modified intermediate for vulcanization, continuously stirring the mixed solution, heating to 148 ℃ for condensation reaction for 3.5 hours, and then carrying out reduced pressure distillation at 128 ℃ by using a vacuum pump to obtain modified imidazoline.
Example 3
An industrial circulating water treatment agent comprises the following raw materials in parts by weight: 1.8 parts of dodecyl dimethyl benzyl ammonium chloride, 30 parts of compound corrosion inhibitor, 21 parts of scale inhibitor, 8 parts of bactericide and 42 parts of water. The compound corrosion inhibitor comprises the following raw materials in parts by weight: 25 parts of modified imidazoline, 10 parts of oxalyl hydrazine compounds, 5 parts of sodium erythorbate, 6 parts of zinc molybdate and 10 parts of D-sodium gluconate; the scale inhibitor comprises the following raw materials in parts by weight: 10 parts of polyacrylic acid, 12 parts of tannic acid and 16 parts of acrylic copolymer; the bactericide comprises the following raw materials in parts by weight: 6 parts of dithiocyano-methane and 12 parts of glutaraldehyde.
The modified imidazoline in the embodiment is prepared by the following steps:
(1) preparing raw materials: 1.5mol of lauric acid, 1mol of ricinoleic acid, 3 mol of diethylenetriamine, 2.5mol of thiosemicarbazide and 35ml of n-octanol;
(2) mixing lauric acid, ricinoleic acid and diethylenetriamine uniformly, adding dimethylbenzene serving as a water carrying agent, stirring, and heating to 150 ℃ in the stirring process to perform amide removal for 2.5 hours; continuously heating to 232 ℃ for cyclodehydration, reacting for 1.8h, cooling to 112 ℃, distilling for 0.5h under reduced pressure by using a vacuum pump to remove xylene and unreacted diethylenetriamine to obtain an intermediate;
(3) heating and stirring the intermediate, dropwise adding anhydrous acetic acid at 52 ℃ to enable the pH to be close to 7, reacting for 0.8h, and cooling to room temperature to obtain a modified intermediate;
(4) and adding thiosemicarbazide and n-octanol into the modified intermediate for vulcanization, continuously stirring the mixed solution, heating to 150 ℃ for condensation reaction for 3 hours, and then carrying out reduced pressure distillation at 128 ℃ by using a vacuum pump to obtain modified imidazoline.
Comparative example 1
This comparative example differs from example 1 in that: the surfactant, dodecyl dimethyl benzyl ammonium chloride, was not added.
Comparative example 2
This comparative example differs from example 1 in that: no oxalyl hydrazine compounds are added into the compound corrosion inhibitor.
Comparative example 3
This comparative example differs from example 1 in that: sodium erythorbate is not added into the compound corrosion inhibitor.
Comparative example 4
This comparative example differs from example 1 in that: no oxalyl hydrazine compounds and sodium erythorbate are added into the compound corrosion inhibitor.
Comparative example 5
This comparative example differs from example 1 in that: tannic acid is not added into the scale inhibitor.
Comparative example 6
This comparative example differs from example 1 in that: the step (3) is not carried out in the process of preparing the modified imidazoline.
Comparative example 7
This comparative example differs from example 1 in that: the step (4) is not carried out in the process of preparing the modified imidazoline.
Test experiments:
the water used in the experiment is circulating water in a circulating water system of a certain automobile part manufacturing factory in Chongqing, and the water quality of the circulating water is shown in the following table through tests:
TABLE 1
The data show that the concentration multiple of the circulating water is about 3 times, the alkalinity and the hardness are slightly high, and the conclusion that the circulating cooling water belongs to scaling type water quality is obtained according to a calculation method of the stability index (S) of the circulating cooling water.
The following tests were carried out on this circulating water:
1. static scale inhibition test
The scale inhibition performance of the circulating water treatment agent in the scheme of the invention is examined through a static scale inhibition test, and the test method refers to a calcium carbonate deposition method for measuring the scale inhibition performance of a water treatment agent (GB/T16632-2008).
Evaporating and concentrating 3 times at 40 ℃, adding a circulating water treatment agent in the scheme of the invention, raising the temperature of a water bath to 80 ℃, standing for 10 hours at constant temperature, and analyzing and determining the content of calcium ions in the clarified liquid. Ca in the test solution2+Was titrated with EDTA standard solution.
Through tests, the scale inhibition effects (scale inhibition rate%) of the circulating water treatment agents of examples 1 to 3 and comparative examples 1 to 7 are obtained as shown in the following table:
TABLE 2
2. Test with rotary hanging strip
The corrosion inhibition performance of the circulating water treatment agent in the scheme of the invention is examined through a rotary hanging piece test. The test method refers to the rotating hanging piece method for measuring the corrosion inhibition performance of the water treatment agent (GB/T18175-2000).
Get on rotatory lacing film corrosion appearance and test with the circulating water, for the operating condition among the simulation recirculating cooling water system, the test block material: q235 steel, test solution temperature: 40. + -. 2 ℃ linear speed of test piece: 0.35 +/-0.2 m/s, and the ratio of the volume of the test solution to the area of the test piece is 35.4mL/cm2(1000mL beaker, individual coupon surface area 30cm2) Single test cycle: and 72 h.
Through tests, the corrosion rates mm/a of the circulating water treatment agents in examples 1-3 and comparative examples 1-7 are obtained, and are shown in the following table:
TABLE 3
Control group: in the rotary hanging test, no circulating water treatment agent is added into the circulating water, and the corrosion speed of the test piece obtained through the test is 0.367 mm/a.
3. Sterilization test
The circulating water treatment agents of examples 1 to 3 and comparative examples 1 to 7 were mixed in an amount of 100 mg. L－1Putting into circulating water for experiment, shaking, placing into a 28-30 deg.C incubator, sampling according to specified time, and analyzing the conditions of heterotrophic bacteria to obtain the following table:
TABLE 4
And (4) experimental conclusion:
1. experimental data of examples 1-3 show that the circulating water treatment agent in the scheme of the invention has good sterilization and scale inhibition performance. When the concentration of the drug is 40 mg.L－1In the case of the scale inhibition rate of 99%, the scale inhibition rate is not in a positive correlation with the input concentration of the chemical, and when the input concentration of the chemical exceeds a certain fixed value, the scale inhibition rate is reduced as the input concentration of the chemical is increased. The circulating water treatment agent also has good corrosion inhibition effect, and compared with the experimental data of examples 1-3 and the data of a control group, the corrosion speed of the circulating water treatment agent added in the scheme is dozens or even dozens of times of that of the circulating water treatment agent added in the scheme without adding the circulating water treatment agent.
2. Comparing the data of the example 1 and the comparative example 1, the corrosion speed of the test piece in the comparative example 1 is obviously higher than that of the example 1, and the sterilization effect of the comparative example 1 is obviously inferior to that of the example 1, so that the quaternary ammonium salt surfactant can be added to improve the corrosion inhibition performance of the medicament, and can be matched with dithiocyano-methane and glutaraldehyde in the bactericide to better exert the sterilization effect of the medicament.
3. Comparing the data of example 1 with comparative example 2, the corrosion rate of the test piece in comparative example 2 is significantly higher than that of example 1, and it can be concluded that: the oxalyl hydrazine compounds have a corrosion inhibition effect on metals, and the corrosion inhibition of the circulating water treatment agent can be effectively improved by adding the oxalyl hydrazine compounds into the compound corrosion inhibitor.
4. Comparing the data of example 1 with that of comparative example 3, the corrosion rate of the test pieces in comparative example 3 is significantly higher than that of example 1, from which it can be concluded: the sodium erythorbate has a corrosion inhibition effect on metals, and the sodium erythorbate is added into the compound corrosion inhibitor, so that the corrosion inhibition of the circulating water treatment agent can be effectively improved.
5. Comparing the data of example 1 with comparative example 4, comparative example 2 with comparative example 4, and comparative example 3 with comparative example 4, the corrosion rate of the test pieces in comparative example 4 is significantly higher than that of example 1, and also significantly higher than that of the test pieces in comparative example 2 and comparative example 3, from which it can be concluded that: the compounding of the oxalyl hydrazine compounds and the sodium erythorbate is beneficial to improving the corrosion inhibition performance of the metal, the compounding of the oxalyl hydrazine compounds and the sodium erythorbate is not simple superposition of the corrosion inhibition performance of the oxalyl hydrazine compounds and the sodium erythorbate, the oxalyl hydrazine compounds and the sodium erythorbate have a synergistic effect, and the corrosion inhibition performance of the metal can be obviously improved.
6. Comparing the data of example 1 and comparative example 5, the scale inhibition rate in comparative example 5 is significantly lower than that of example 1 and the corrosion rate of the test piece in comparative example 5 is significantly higher than that of example 1, so that it is known that the addition of tannic acid not only can increase the scale inhibition rate, but also can improve the corrosion inhibition effect of the chemical.
7. Comparing the data of example 1 with comparative example 6, the corrosion rate of the test pieces in comparative example 6 is significantly higher than that of example 1, thus proving that: through the treatment in the step (3), imidazoline can obtain enough hydrophilic groups, the water solubility of the modified imidazoline is greatly improved, the modified imidazoline can be better applied to circulating water, and the corrosion inhibition of the agent is enhanced.
8. Comparing the data of example 1 with comparative example 7, the corrosion rate of the test pieces in comparative example 7 is significantly higher than that of example 1, thus proving that: the modified intermediate is subjected to vulcanization treatment, so that the binding capacity of the modified imidazoline and metal can be enhanced, a stable adsorption film can be formed, and the corrosion inhibition effect of the modified imidazoline is ensured.
Claims (5)
1. An industrial circulating water treatment agent is characterized in that: the composite material comprises the following raw materials in parts by mass: 0.8-1.8 parts of surfactant, 26-32 parts of compound corrosion inhibitor, 17-23 parts of scale inhibitor, 4-8 parts of bactericide and 40-50 parts of water; the compound corrosion inhibitor comprises the following raw materials in parts by weight: 24-28 parts of modified imidazoline, 9-12 parts of oxalyl hydrazine compounds, 2-5 parts of sodium erythorbate, 6-9 parts of zinc salt and 10-12 parts of gluconate; the scale inhibitor comprises the following raw materials in parts by weight: 5-12 parts of polyacrylic acid, 8-15 parts of tannic acid and 8-16 parts of acrylic copolymer;
the modified imidazoline is prepared by the following steps:
(1) preparing raw materials: 1.2-2mol of lauric acid, 0.4-1mol of ricinoleic acid, 2-3.2mol of diethylenetriamine, 1.8-2.4mol of thiosemicarbazide and 30-40ml of n-octanol;
(2) uniformly mixing lauric acid, ricinoleic acid and diethylenetriamine, adding dimethylbenzene serving as a water carrying agent, stirring, and heating to the temperature of 140-; continuously heating to 225-245 ℃ for cyclodehydration, reacting for 1.5-2h, cooling to 110-120 ℃, and removing xylene and unreacted diethylenetriamine through reduced pressure distillation to obtain an intermediate;
(3) heating and stirring the intermediate, dropwise adding anhydrous acetic acid at 48-53 ℃ to enable the pH to be close to 7, reacting for 0.5-1h, and cooling to room temperature to obtain a modified intermediate;
(4) and adding thiosemicarbazide and n-octanol into the modified intermediate for vulcanization treatment, continuously stirring the mixed solution, heating to 160 ℃ for condensation reaction for 3-4h, and then performing reduced pressure distillation at 132 ℃ by using a vacuum pump to obtain the modified imidazoline.
2. The industrial circulating water treatment agent as claimed in claim 1, wherein: the gluconate is D-sodium gluconate or D-potassium gluconate.
3. The industrial circulating water treatment agent as claimed in claim 1, wherein: the relative molecular mass of the polyacrylic acid is 2000-3000.
4. The industrial circulating water treatment agent as claimed in claim 1, wherein: the bactericide comprises the following raw materials in parts by weight: 5-8 parts of dithiocyano-methane and 6-12 parts of glutaraldehyde.
5. The industrial circulating water treatment agent as claimed in claim 1, wherein: the surfactant is quaternary ammonium salt surfactant, and is one or more of dodecyl dimethyl benzyl ammonium chloride, polyquaternary ammonium salt, and tetradecyl dimethyl benzyl ammonium chloride.
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