CN110330122B - Multifunctional environment-friendly water treatment agent and preparation method thereof - Google Patents
Multifunctional environment-friendly water treatment agent and preparation method thereof Download PDFInfo
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- CN110330122B CN110330122B CN201910461220.7A CN201910461220A CN110330122B CN 110330122 B CN110330122 B CN 110330122B CN 201910461220 A CN201910461220 A CN 201910461220A CN 110330122 B CN110330122 B CN 110330122B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
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- C—CHEMISTRY; METALLURGY
- 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
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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
- C02F2303/04—Disinfection
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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
Abstract
The invention relates to the technical field of water treatment, in particular to a multifunctional environment-friendly water treatment agent and a preparation method thereof, wherein the formula of the multifunctional environment-friendly water treatment agent is prepared from 20-60% of modified nano cellulose quaternary ammonium salt mixed solution, 5-40% of oxidized nano cellulose mixed solution, 10-30% of alkylamine emulsion and 2-10% of betaine type surfactant. The water treatment agent disclosed by the invention contains a large number of active groups such as amino, carboxyl, sulfonic group, hydroxyl, quaternary ammonium salt cations and the like, can simultaneously realize multiple effects such as cleaning, corrosion inhibition, scale inhibition, sterilization, dispersion and the like through the synergistic effect of the active groups, has the advantages of biodegradability, no phosphorus, environmental friendliness, low-price and easily-obtained raw materials, is suitable for fresh water circulating cooling water and seawater circulating cooling water, and has a very good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a multifunctional environment-friendly water treatment agent and a preparation method thereof.
Background
China is one of countries with water resource shortage and serious pollution, the industrial water consumption is increasing with the rapid development of industrial production, and the cooling water accounts for more than 80% of the industrial water. The cooling water is continuously circulated and concentrated when in use, various substances are deposited on the heat exchanger and the inner wall of the system in the operation process (for example, inorganic salts such as calcium carbonate and the like are attached to the heat exchanger to be supersaturated and separated out, and can be firmly attached to the heat transfer surface of the heat exchanger to form hard scale, microorganisms and viscous secretion thereof in water are combined with fine silt, dust, oil stain and mud of other insoluble salts to form soft scale (or called biological viscous mud), the deposits influence the heat exchange effect and aggravate the corrosion of the system at the same time to cause the problems of scaling, corrosion, microorganism breeding and the like of the equipment pipeline, the heat transfer efficiency is reduced slightly, and production accidents are caused seriously. Therefore, industrial cooling water is generally required to use a water treatment agent for keeping the system clean, preventing corrosion and scale formation of metal pipes, and the like.
At present, a water treatment agent mainly comprises a prefilming agent, a corrosion and scale inhibitor, a sterilization and mildew inhibitor and the like, and is added according to actual working conditions. The corrosion and scale inhibitor mainly comprises a phosphorus formula, a molybdenum formula, an organic phosphorus formula, a silicon formula and the like. Phosphorus and organic phosphine formulas have good corrosion and scale inhibition effects, but phosphorus can cause water eutrophication and easily generates calcium phosphate, and measures such as phosphorus prohibition, phosphorus limitation and the like have been proposed in many countries; the molybdate corrosion and scale inhibitor belongs to a low-toxicity and pollution-free compound, has good corrosion inhibition effect, but has higher cost and is a non-renewable resource, so the molybdate corrosion and scale inhibitor is limited in use and is difficult to popularize and use in industrial water; the silicate slow-release scale inhibitor has low price and no toxicity, but has unstable performance and is easy to form silica scale. In the prior art, a macromolecular slow-release scale inhibitor such as polyacrylic acid is also adopted, but the macromolecular polymer and the copolymer are not easy to biodegrade and are not beneficial to environmental protection; in addition, zinc salts are also used as corrosion and scale inhibitors in various corrosion and scale inhibitors in the prior art, but the national emission of the zinc salts has concentration limitation.
With the increasing requirements of people on environmental protection, the development of water treatment agents is also more and more prone to low-toxicity, non-toxic and easily biodegradable high molecular substances. However, the use of a high molecular weight material alone as a scale and corrosion inhibitor is inefficient and requires modification or other treatment. Therefore, there is a need to research and develop a water treatment agent which has multiple functions of cleaning, corrosion inhibition, scale inhibition, sterilization and the like, is easily biodegradable, is environment-friendly and can realize industrial application.
Disclosure of Invention
The invention aims to provide an environment-friendly water treatment agent which has multiple functions of cleaning, corrosion inhibition, scale inhibition, sterilization and the like and is easy to biodegrade and a preparation method thereof aiming at the defects in the prior art.
The purpose of the invention is realized by the following technical scheme:
provides a multifunctional environment-friendly water treatment agent, which is characterized in that: the material is prepared from the following raw materials in percentage by mass:
in the technical scheme, the multifunctional environment-friendly water treatment agent is prepared from the following raw materials in percentage by mass:
in the technical scheme, the modified nano-cellulose quaternary ammonium salt mixed solution is prepared by modifying nano-cellulose, monochloroacetic acid, polyquaternary ammonium salt and an initiator, wherein the nano-cellulose: monochloroacetic acid: the mass ratio of the polyquaternium to the polyquaternium is 1 (0.5-2) to 1-6, and the dosage of the initiator is 0.01-0.2% of the total mass of the nano-cellulose.
In the technical scheme, the polyquaternary ammonium salt is at least one of polymethacryloxyethyltrimethyl ammonium chloride, polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, polyoxyethylene halogenated dimethylammonium chloride, polydimethyldiallylammonium chloride and polydimethyldiallylammonium bromide; the initiator is ammonium persulfate or potassium persulfate.
In the technical scheme, the oxidized nano-cellulose mixed solution is obtained by oxidizing nano-cellulose, ferrous sulfate and hydrogen peroxide, wherein the mass ratio of the hydrogen peroxide to the nano-cellulose is (20-75): 100, and the mass ratio of the ferrous sulfate to the nano-cellulose is (0.8-2.6): 100.
In the technical scheme, the alkylamine emulsion is obtained by carrying out an emulsion reaction on alkylamine, an emulsifier and water, wherein the mass ratio of the alkylamine to the emulsifier to the water is (3-50): (1-10): (40-96).
In the above technical scheme, the alkylamine is R1NH2、R1R2NH、R1R2R3N、R1NHR4NH2Or R1NHR4NHR5NH2Wherein R is1、R2、R3、R4、R5All are C1-24Linear or branched alkanes.
In the technical scheme, the emulsifier is at least one of fatty amine polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyethylene glycol, span and Tween.
In the technical scheme, the betaine surfactant is RN+(CH3)2CH2COO-、RCONH(CH2)3N+(CH3)2CH2COO-、RN+(CH3)2(CH2)3SO3 -、RN+(CH3)2CH2CH(OH)CH2SO3 -、RN(CH3)2CH2CH(OH)CH2HPO4Wherein R is C12-18Linear or branched alkanes.
The invention also provides a preparation method of the multifunctional environment-friendly water treatment agent, which comprises the following steps:
step a, preparing a modified nano cellulose quaternary ammonium salt mixed solution:
firstly dispersing nano-cellulose in a tetrahydrofuran-sodium hydroxide mixed solution, heating to 50-60 ℃, stirring for pretreatment for 1-2h, then adding monochloroacetic acid, reacting for 4-6h at 60-80 ℃, adding a hydrochloric acid solution to adjust the pH value to 7, then adding an initiator under the stirring condition, gradually adding polyquaternium, and reacting for 3-6h at 60-80 ℃ to obtain a modified nano-cellulose quaternary ammonium salt mixed solution;
in this step, the nanocellulose: monochloroacetic acid: the mass ratio of the polyquaternium to the polyquaternium is 1 (0.5-2) to 1-5, and the using amount of the initiator is 0.01-0.2% of the total mass of the nano-cellulose;
step b, preparing oxidized nano cellulose mixed liquor:
adding nano-cellulose, isopropanol and water into a reaction kettle, heating to 70-90 ℃, stirring for 0.5-1h, then adding ferrous sulfate while stirring, slowly adding hydrogen peroxide, and reacting for 1-3h to obtain oxidized nano-cellulose mixed solution;
in the step, the mass ratio of the hydrogen peroxide to the nano-cellulose is (20-75): 100, and the mass ratio of the ferrous sulfate to the nano-cellulose is (0.8-2.6): 100;
step c, preparing alkylamine emulsion:
heating and melting alkylamine and emulsifier, uniformly stirring, slowly adding water, and uniformly stirring to obtain alkylamine emulsion;
in the step, the mass ratio of the alkylamine to the emulsifier to the water is (3-50) to (1-10) to (40-96);
step d, mixing:
respectively placing the prepared modified nano cellulose quaternary ammonium salt mixed solution, oxidized nano cellulose mixed solution, alkylamine emulsion and betaine type surfactant into a reaction kettle according to the formula amount, stirring for 0.5-1h at 15-35 ℃, and uniformly stirring to obtain the multifunctional environment-friendly water treatment agent.
The invention has the beneficial effects that:
the invention relates to a preparation method of a multifunctional environment-friendly water treatment agent, which is prepared from 20-60% of modified nano cellulose quaternary ammonium salt mixed solution, 5-40% of oxidized nano cellulose mixed solution, 10-30% of alkylamine emulsion and 2-10% of betaine type surfactant. Compared with the prior art, the invention has the following advantages:
(1) the water treatment agent contains a large amount of active groups such as amino, carboxyl, sulfonic group, hydroxyl, quaternary ammonium salt cation and the like; wherein the carboxyl group and sulfonic acid group can be bonded with scale-forming metal ions such as Ca2+、Mg2+The metal ions are combined into a metal ion chelate, and the growth of dirt can be inhibited through the lattice distortion effect; the polyquaternium not only has the sterilization and biocidal effects, but also can adsorb and remove part of chloride ions in the circulating water, and has stronger stripping and dispersing effects on slime; the alkylamine has affinity with metal, can form a smooth protective film on the inner wall surfaces of metal, concrete and the like, isolates the contact between dissolved oxygen in water and ions and the metal, and plays a role in preventing or slowing down the corrosion of the metal; through the synergistic effect of the active groups, on one hand, the water treatment agent gradually flocculates and settles in a water pool by catching supersaturated calcium salt and suspended substances, thereby achieving the effects of reducing turbidity and hardness; on the other hand, soft scale is deposited in the dispersion stripping system under the action of water flow; the hard scale is gradually moistened and fluffy to become soft scale and then gradually peeled off, and finally, corrosion inhibition and inhibition can be simultaneously realizedScale removing, sterilization, dispersion and other multiple effects, so that the effect of self-cleaning of the system is achieved;
(2) the water treatment agent disclosed by the invention does not contain phosphorus, can avoid water eutrophication and calcium phosphate scale;
(3) the raw materials of the invention adopt biodegradable natural polymer, which is an environment-friendly water treatment agent, and the invention has the advantages of low price, easy obtainment, simple preparation process and easy control;
(4) the water treatment agent has wide application range, the polyquaternium is also a good marine organism biocide, and the betaine type surfactant keeps good dispersion and scale inhibition performance on a high-salinity water system; therefore, the invention is not only suitable for fresh water circulating cooling water, but also suitable for seawater circulating cooling water, and has very good industrial application prospect.
Detailed Description
The invention is further described with reference to the following examples.
Example 1:
the preparation method of the multifunctional environment-friendly water treatment agent comprises the following steps:
step a, preparing a modified nano cellulose quaternary ammonium salt mixed solution:
firstly dispersing nano-cellulose in a tetrahydrofuran-sodium hydroxide mixed solution, heating to 50 ℃, stirring for pretreatment for 2h, then adding monochloroacetic acid, reacting for 6h at 60 ℃, adding a hydrochloric acid solution to adjust the pH value to 7, then adding ammonium persulfate under the stirring condition, gradually adding polyhexamethylene guanidine hydrochloride and polyhexamethylene biguanide hydrochloride, and reacting for 6h at 60 ℃ to obtain a modified nano-cellulose quaternary ammonium salt mixed solution;
in the step, in a tetrahydrofuran-sodium hydroxide mixed solution, the volume ratio of tetrahydrofuran to 20% sodium hydroxide is 1:1, and the concentration of nano-cellulose in the mixed solution is 0.1 g/ml;
nano-cellulose: monochloroacetic acid: polyhexamethylene guanidine hydrochloride: the mass ratio of the polyhexamethylene biguanide hydrochloride is 1:1:1:5, and the dosage of the ammonium persulfate is 0.08 percent of the total mass of the nano-cellulose.
Step b, preparing oxidized nano cellulose mixed liquor:
adding nano-cellulose, isopropanol and water into a reaction kettle, heating to 70 ℃, stirring for 1h, then adding ferrous sulfate accounting for 20% of the mass of the nano-cellulose while stirring, then slowly adding hydrogen peroxide accounting for 0.8% of the mass of the nano-cellulose, and reacting for 3h to obtain oxidized nano-cellulose mixed solution;
in the step, the volume ratio of isopropanol to water is 1:1, and the concentration of the nano-cellulose in the mixed solution of isopropanol and water is 0.1 g/ml.
Step c, preparing alkylamine emulsion:
heating and melting octadecylamine and fatty amine polyoxyethylene ether, uniformly stirring, slowly adding water, and uniformly stirring to obtain alkylamine emulsion;
in this step, octadecyl amine: fatty amine polyoxyethylene ether: the mass ratio of water is 5:4: 45.
Step d, mixing:
respectively weighing 30g of prepared modified nano cellulose quaternary ammonium salt mixed solution, 10g of oxidized nano cellulose mixed solution, 15g of alkylamine emulsion and 4g of betaine type surfactant, placing the obtained mixture in a reaction kettle, stirring the obtained mixture for 1 hour at 15 ℃, and uniformly stirring the obtained product to obtain the multifunctional environment-friendly water treatment agent;
in this step, the betaine type surfactant is RN+(CH3)2CH2COO-Wherein R is C12-18Linear or branched alkanes.
Example 2:
the preparation method of the multifunctional environment-friendly water treatment agent comprises the following steps:
step a, preparing a modified nano cellulose quaternary ammonium salt mixed solution:
firstly dispersing nano-cellulose in a tetrahydrofuran-sodium hydroxide mixed solution, heating to 60 ℃, stirring for pretreatment for 1h, then adding monochloroacetic acid, reacting for 4h at 80 ℃, adding a hydrochloric acid solution to adjust the pH value to 7, then adding potassium persulfate under the stirring condition, gradually adding polymethacryloxyethyl trimethyl ammonium chloride, and reacting for 3h at 80 ℃ to obtain a modified nano-cellulose quaternary ammonium salt mixed solution;
in the step, in the mixed solution of tetrahydrofuran and sodium hydroxide, the volume ratio of tetrahydrofuran to 30% sodium hydroxide is 3:2, and the concentration of nano-cellulose in the mixed solution is 0.2 g/ml;
nano-cellulose: monochloroacetic acid: the mass ratio of the polymethacryloxyethyltrimethyl ammonium chloride is 1:1.2:5, and the dosage of the potassium persulfate is 0.2 percent of the total mass of the nano-cellulose.
Step b, preparing oxidized nano cellulose mixed liquor:
adding nano-cellulose, isopropanol and water into a reaction kettle, heating to 90 ℃, stirring for 0.5h, then adding ferrous sulfate accounting for 75% of the mass of the nano-cellulose while stirring, then slowly adding hydrogen peroxide accounting for 2.6% of the mass of the nano-cellulose, and reacting for 1h to obtain oxidized nano-cellulose mixed solution;
in the step, the volume ratio of isopropanol to water is 2:3, and the concentration of the nano-cellulose in the mixed solution of isopropanol and water is 0.15 g/ml.
Step c, preparing alkylamine emulsion:
heating and melting dodecyl dimethyl tertiary amine and polyethylene glycol, uniformly stirring, slowly adding water, and uniformly stirring to obtain alkylamine emulsion;
in this step, dodecyl dimethyl tertiary amine: polyethylene glycol: the mass ratio of water is 30:8: 90.
Step d, mixing:
respectively weighing 50g of prepared modified nano cellulose quaternary ammonium salt mixed solution, 30g of oxidized nano cellulose mixed solution, 25g of alkylamine emulsion and 8g of betaine type surfactant, putting the obtained mixture into a reaction kettle, stirring the obtained mixture for 0.5h at the temperature of 35 ℃, and uniformly stirring the obtained mixture to obtain the multifunctional environment-friendly water treatment agent;
in this step, the betaine type surfactant is RCONH (CH)2)3N+(CH3)2CH2COO-Wherein R is C12-18Linear or branched alkanes.
Example 3:
the preparation method of the multifunctional environment-friendly water treatment agent comprises the following steps:
step a, preparing a modified nano cellulose quaternary ammonium salt mixed solution:
firstly dispersing nano-cellulose in a tetrahydrofuran-sodium hydroxide mixed solution, heating to 56 ℃, stirring for pretreatment for 1.3h, then adding monochloroacetic acid, reacting for 5h at 72 ℃, adding a hydrochloric acid solution to adjust the pH value to 7, then adding ammonium persulfate under the stirring condition, gradually adding polydimethyldiallylammonium bromide, and reacting for 4h at 72 ℃ to obtain a modified nano-cellulose quaternary ammonium salt mixed solution;
in the step, in a tetrahydrofuran-sodium hydroxide mixed solution, the volume ratio of tetrahydrofuran to 15% of sodium hydroxide in mass concentration is 1:2, and the concentration of nano-cellulose in the mixed solution is 0.15 g/ml;
nano-cellulose: monochloroacetic acid: the mass ratio of the poly dimethyl diallyl ammonium bromide is 1:0.5:3, and the using amount of the ammonium persulfate is 0.09% of the total mass of the nano-cellulose.
Step b, preparing oxidized nano cellulose mixed liquor:
adding nano-cellulose, isopropanol and water into a reaction kettle, heating to 85 ℃, stirring for 0.6h, then adding ferrous sulfate accounting for 35% of the mass of the nano-cellulose while stirring, then slowly adding hydrogen peroxide accounting for 1.3% of the mass of the nano-cellulose, and reacting for 2h to obtain oxidized nano-cellulose mixed solution;
in the step, the volume ratio of isopropanol to water is 1:2, and the concentration of the nano-cellulose in the mixed solution of isopropanol and water is 0.18 g/ml.
Step c, preparing alkylamine emulsion:
firstly, heating and melting alkylamine, emulsifier span S-80 and Tween T-80, uniformly stirring, slowly adding water, and uniformly stirring to obtain alkylamine emulsion;
in this step, alkylamine: span S-80: tween T-80: the mass ratio of water is 45:4:2: 75; wherein, the alkylamine has a structural formula of CH3NHCH2NH(CH2)3NH2。
Step d, mixing:
respectively weighing 40g of prepared modified nano cellulose quaternary ammonium salt mixed solution, 25g of oxidized nano cellulose mixed solution, 30g of alkylamine emulsion and 5g of betaine type surfactant, putting the obtained mixture into a reaction kettle, stirring the obtained mixture for 0.6h at 25 ℃, and uniformly stirring the obtained mixture to obtain the multifunctional environment-friendly water treatment agent;
in this step, the betaine type surfactant is composed of RN+(CH3)2(CH2)3SO3 -And RN+(CH3)2CH2CH(OH)CH2SO3 -Is compounded according to the mass ratio of 2:1, wherein R is C12-18Linear or branched alkanes.
Example 4:
the preparation method of the multifunctional environment-friendly water treatment agent comprises the following steps:
step a, preparing a modified nano cellulose quaternary ammonium salt mixed solution:
firstly dispersing nano-cellulose in a tetrahydrofuran-sodium hydroxide mixed solution, heating the nano-cellulose to 53 ℃, stirring for pretreatment for 1.8h, then adding monochloroacetic acid, reacting for 5.5h at 66 ℃, adding a hydrochloric acid solution to adjust the pH value to 7, then adding potassium persulfate under the stirring condition, gradually adding polyquaternium, and reacting for 5h at 66 ℃ to obtain a modified nano-cellulose quaternary ammonium salt mixed solution;
in the step, in the mixed solution of tetrahydrofuran and sodium hydroxide, the volume ratio of tetrahydrofuran to 22% sodium hydroxide is 1:1, and the concentration of nano-cellulose in the mixed solution is 0.18 g/ml;
nano-cellulose: monochloroacetic acid: the mass ratio of the polyquaternium is 1:1.6:1, the dosage of the potassium persulfate is 0.01 percent of the total mass of the nano-cellulose, wherein the polyquaternium is prepared by compounding poly (methacryloyloxyethyl trimethyl ammonium chloride), poly (oxyethylene) halogenated dimethyl ammonium sulfite and poly (dimethyl diallyl ammonium chloride) according to the mass ratio of 1:2: 1.
Step b, preparing oxidized nano cellulose mixed liquor:
adding nano-cellulose, isopropanol and water into a reaction kettle, heating to 78 ℃, stirring for 0.8h, then adding ferrous sulfate accounting for 60% of the mass of the nano-cellulose while stirring, then slowly adding hydrogen peroxide accounting for 2.2% of the mass of the nano-cellulose, and reacting for 2.2h to obtain oxidized nano-cellulose mixed solution;
in the step, the volume ratio of isopropanol to water is 3:2, and the concentration of the nano-cellulose in the mixed solution of isopropanol and water is 0.2 g/ml.
Step c, preparing alkylamine emulsion:
heating and melting alkylamine and fatty alcohol-polyoxyethylene ether, uniformly stirring, slowly adding water, and uniformly stirring to obtain alkylamine emulsion;
in this step, alkylamine: fatty alcohol polyoxyethylene ether: the mass ratio of water is 20:2:60, wherein the structural formula of alkylamine is (CH)3)3CNH(CH2)11CH3。
Step d, mixing:
respectively weighing 60g of prepared modified nano cellulose quaternary ammonium salt mixed solution, 40g of oxidized nano cellulose mixed solution, 10g of alkylamine emulsion and 6g of betaine type surfactant, putting the obtained mixture into a reaction kettle, stirring the obtained mixture for 0.8h at the temperature of 30 ℃, and uniformly stirring the obtained mixture to obtain the multifunctional environment-friendly water treatment agent;
in this step, the betaine type surfactant is RN (CH)3)2CH2CH(OH)CH2HPO4Wherein R is C12-18Linear or branched alkanes.
Test example:
the following tests are provided to illustrate the corrosion and scale inhibiting effects of the present invention.
With reference to chemical industry standard HG/T2160-2008 cooling water dynamic simulation test method, the multifunctional environment-friendly water treatment agent obtained in examples 1 to 4 was subjected to a dynamic simulation test:
the mass concentration of the multifunctional environment-friendly water treatment agent in water is controlled to be 100mg/L, a heat exchanger test tube is a 316L stainless steel test tube with phi 19 x 2 x 1250mm, a test water passing tube pass added with the water treatment agent is heated by saturated steam, the water inlet temperature of the test water is controlled to be 30 +/-1 ℃, the temperature difference between an inlet and an outlet is 10 ℃, and the flow speed is 0.6-1.2 m/s;
the test water is power plant water, the make-up water is mixed water of industrial sewage, domestic sewage and reclaimed water, and the detection parameters of the quality of the make-up water are as follows: total hardness of 302.25mg/L, total alkalinity of 289.08mg/L and mass concentration of chloride ion of 176.62 mg/L. The test was run continuously for 27 days with a circulating water concentration factor (8. + -. 0.5 based on the water content).
The corrosion rate (national standard) is measured by a coupon method, and the test piece comprises A3Carbon steel, brass, and 316L stainless steel. The test structure is shown in table 1:
TABLE 1 Corrosion and Scale inhibition Effect of the multifunctional Environment-friendly Water treatment agent of examples 1 to 4
As can be seen from Table 1, the corrosion rates of the recirculated cooling water to which the multifunctional environmental protection water treatment agents of examples 1 to 4 were added were respectively as follows:
A3carbon steel: 0.0122-0.036mm/a, brass: 0.0003-0.0008mm/a, 316L stainless steel: 0.0000 mm/a; the corrosion rate of the composite material is far lower than the national standard requirement of the design code of industrial circulating cooling water treatment (GB 50050-2017). The dirt deposition rate is 6.003-6.016mg/cm2Monthly, less than 15mg/cm required by national standards2Month.
Test results show that the multifunctional environment-friendly water treatment agent has good corrosion and scale inhibition effects.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the present invention.
Claims (10)
1. A multifunctional environment-friendly water treatment agent is characterized in that: the material is prepared from the following raw materials in percentage by mass:
the preparation method of the modified nano cellulose quaternary ammonium salt mixed solution comprises the following steps: firstly dispersing nano-cellulose in a tetrahydrofuran-sodium hydroxide mixed solution, heating to 50-60 ℃, stirring for pretreatment for 1-2h, then adding monochloroacetic acid, reacting for 4-6h at 60-80 ℃, adding a hydrochloric acid solution to adjust the pH value to 7, then adding an initiator under the stirring condition, gradually adding polyquaternium, and reacting for 3-6h at 60-80 ℃ to obtain a modified nano-cellulose quaternary ammonium salt mixed solution;
the preparation method of the oxidized nano-cellulose mixed solution comprises the following steps:
adding nano-cellulose, isopropanol and water into a reaction kettle, heating to 70-90 ℃, stirring for 0.5-1h, then adding ferrous sulfate while stirring, slowly adding hydrogen peroxide, and reacting for 1-3h to obtain oxidized nano-cellulose mixed solution;
the preparation method of the alkylamine emulsion comprises the following steps:
firstly, heating and melting alkylamine and emulsifier, uniformly stirring, slowly adding water, and uniformly stirring to obtain alkylamine emulsion.
2. The multifunctional environment-friendly water treatment agent according to claim 1, wherein: the material is prepared from the following raw materials in percentage by mass:
3. the multifunctional environment-friendly water treatment agent according to claim 1 or 2, wherein: the modified nano-cellulose quaternary ammonium salt mixed solution is prepared by modifying nano-cellulose, monochloroacetic acid, polyquaternary ammonium salt and an initiator, wherein the nano-cellulose: monochloroacetic acid: the mass ratio of the polyquaternium to the polyquaternium is 1 (0.5-2) to 1-6, and the dosage of the initiator is 0.01-0.2% of the total mass of the nano-cellulose.
4. The multifunctional environment-friendly water treatment agent according to claim 3, wherein: the polyquaternary ammonium salt is at least one of polymethacryloxyethyltrimethyl ammonium chloride, polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, polyoxyethylene halogenated dimethylammonium, polydimethyldiallylammonium chloride and polydimethyldiallylammonium bromide; the initiator is ammonium persulfate or potassium persulfate.
5. The multifunctional environment-friendly water treatment agent according to claim 1 or 2, wherein: the oxidized nano-cellulose mixed solution is obtained by oxidizing nano-cellulose, ferrous sulfate and hydrogen peroxide, wherein the mass ratio of the hydrogen peroxide to the nano-cellulose is (20-75): 100, and the mass ratio of the ferrous sulfate to the nano-cellulose is (0.8-2.6): 100.
6. The multifunctional environment-friendly water treatment agent according to claim 1 or 2, wherein: the alkylamine emulsion is obtained by carrying out an emulsion reaction on alkylamine, an emulsifier and water, wherein the mass ratio of the alkylamine to the emulsifier to the water is (3-50): (1-10): (40-96).
7. The multifunctional environment-friendly water treatment agent according to claim 6, wherein: the alkylamine is R1NH2、R1R2NH、R1R2R3N、R1NHR4NH2Or R1NHR4NHR5NH2Wherein R is1、R2、R3、R4、R5All are C1-24Linear or branched alkanes.
8. The multifunctional environment-friendly water treatment agent according to claim 6, wherein: the emulsifier is at least one of fatty amine polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyethylene glycol, span and Tween.
9. The multifunctional environment-friendly water treatment agent according to claim 1 or 2, wherein: the betaine surfactant is RN+(CH3)2CH2COO-、RCONH(CH2)3N+(CH3)2CH2COO-、RN+(CH3)2(CH2)3SO3 -、RN+(CH3)2CH2CH(OH)CH2SO3 -、RN(CH3)2CH2CH(OH)CH2HPO4Wherein R is C12-18Linear or branched alkanes.
10. The method for preparing a multifunctional environment-friendly water treatment agent as claimed in any one of claims 1 to 9, wherein: the method comprises the following steps:
step a, preparing a modified nano cellulose quaternary ammonium salt mixed solution:
firstly dispersing nano-cellulose in a tetrahydrofuran-sodium hydroxide mixed solution, heating to 50-60 ℃, stirring for pretreatment for 1-2h, then adding monochloroacetic acid, reacting for 4-6h at 60-80 ℃, adding a hydrochloric acid solution to adjust the pH value to 7, then adding an initiator under the stirring condition, gradually adding polyquaternium, and reacting for 3-6h at 60-80 ℃ to obtain a modified nano-cellulose quaternary ammonium salt mixed solution;
in this step, the nanocellulose: monochloroacetic acid: the mass ratio of the polyquaternium to the polyquaternium is 1 (0.5-2) to 1-5, and the using amount of the initiator is 0.01-0.2% of the total mass of the nano-cellulose;
step b, preparing oxidized nano cellulose mixed liquor:
adding nano-cellulose, isopropanol and water into a reaction kettle, heating to 70-90 ℃, stirring for 0.5-1h, then adding ferrous sulfate while stirring, slowly adding hydrogen peroxide, and reacting for 1-3h to obtain oxidized nano-cellulose mixed solution;
in the step, the mass ratio of the hydrogen peroxide to the nano-cellulose is (20-75): 100, and the mass ratio of the ferrous sulfate to the nano-cellulose is (0.8-2.6): 100;
step c, preparing alkylamine emulsion:
heating and melting alkylamine and emulsifier, uniformly stirring, slowly adding water, and uniformly stirring to obtain alkylamine emulsion;
in the step, the mass ratio of the alkylamine to the emulsifier to the water is (3-50) to (1-10) to (40-96);
step d, mixing:
respectively placing the prepared modified nano cellulose quaternary ammonium salt mixed solution, oxidized nano cellulose mixed solution, alkylamine emulsion and betaine type surfactant into a reaction kettle according to the formula amount, stirring for 0.5-1h at 15-35 ℃, and uniformly stirring to obtain the multifunctional environment-friendly water treatment agent.
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