CN113880265A - Phosphorus-free corrosion and scale inhibitor and preparation method thereof - Google Patents
Phosphorus-free corrosion and scale inhibitor and preparation method thereof Download PDFInfo
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- CN113880265A CN113880265A CN202111237989.4A CN202111237989A CN113880265A CN 113880265 A CN113880265 A CN 113880265A CN 202111237989 A CN202111237989 A CN 202111237989A CN 113880265 A CN113880265 A CN 113880265A
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- sorbitol
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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
- 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
- C02F5/105—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 combined with inorganic substances
Abstract
The invention provides a phosphorus-free corrosion and scale inhibitor, which consists of sorbitol maleate mixture, zinc chloride, poly dimethyl diallyl ammonium chloride and benzotriazole, wherein the molar ratio of sorbitol maleate monoester to sorbitol diester to sorbitol in the sorbitol maleate mixture is 0.2-0.6: 1: within the range of 0.2-0.5, the three components form an annular stable structure by hydrogen bonds, and the three components cooperate with each other to greatly increase the chelating and dispersing capacity to scale ions such as calcium, magnesium and the like, and can form a film layer on the surface of the metal, so that the film layer has better corrosion inhibition performance to the metal. The zinc chloride and the benzotriazole can promote a ring structure and a metal chelating substance to be more stable into a film layer structure, so that the zinc chloride and the benzotriazole cooperate with each other to improve the corrosion inhibition performance of the product, and the poly-dimethyl diallyl ammonium chloride can promote corrosion inhibition and sterilization and algae removal performance. The components in the scale inhibitor are easy to obtain, the preparation conditions are mild, the synergistic capability of the components in the scale inhibitor is strong, and the scale inhibitor has good popularization and application values.
Description
Technical Field
The invention belongs to the technical field of circulating cooling water, and particularly relates to a phosphorus-free corrosion and scale inhibitor.
Background
The recycling of industrial cooling water is the most effective technical scheme for industrial water saving and is also a typical energy-saving and emission-reducing measure. Because of the natural evaporation of water in the water storage tank and the cooling tower during cooling, the concentration of salt dissolved in the circulating cooling water is increased, and the concentration multiple of common industrial cooling water is 3-5 times, so that salt is easy to form dirt on the heat transfer surface of the cooled equipment, and the heat transfer rate of the equipment is greatly reduced, so that the temperature change of the production process materials influences the normal production. The temperature of the general circulating cooling water is just the condition that the bacteria and algae which can be attached to the heat transfer surface in the water and live are easy to breed, the metabolite of the circulating cooling water is easy to corrode the metal heat transfer surface, and the metal is corroded by the overhigh salt concentration, so the service life of the heat transfer equipment is greatly reduced, and the production cost is improved. The addition of proper amount of corrosion and scale inhibitor into the circulating cooling water can make the salt maintain dispersion state at high concentration to prevent the formation of scale layer on the heat transfer surface and form protecting film on the heat transfer surface, and reduce the growth of bacteria and algae to delay the corrosion of the apparatus. The phosphorus-containing corrosion and scale inhibitor is easy to cause environmental pollution caused by eutrophication of final sewage, and the development of the economic and degradable green environment-friendly phosphorus-free corrosion and scale inhibitor is the development direction of the field.
CN106745852A discloses a phosphorus-free corrosion and scale inhibitor, which comprises the following formula components in parts by mass: 6-8 parts of lignosulfonate, 5-7 parts of hydrolyzed polymaleic anhydride, 5-9 parts of citrate, 6-8 parts of triethanolamine, 6-8 parts of tannin, 2-4 parts of zinc salt, 5-7 parts of polyepoxysuccinic acid, 4-6 parts of sodium polyacrylate, 4-6 parts of sodium humate, 6-10 parts of zinc sulfate, 6-8 parts of benzotriazole and 2-4 parts of distilled water.
CN100509652C relates to a phosphorus-free corrosion and scale inhibitor used in circulating cooling water, which is prepared by mixing the following raw materials: 1) polyaspartic acid or/and polyepoxysuccinic acid, 2) polymaleic anhydride, 3) acrylic acid/2-acrylamide-2-methacrylic sulfonic acid copolymer, 4) zinc salt, 5) natural organic polymer, 6) molybdate and 7) other components. The phosphorus-free corrosion and scale inhibitor has excellent corrosion and scale inhibition performance and good environmental protection performance.
CN200510070652.3 discloses a corrosion and scale inhibition technology for copper and copper alloy equipment in a cooling water system, wherein an oil-soluble corrosion inhibitor comprises sorbitan carboxylic ester, and a water-soluble dispersant comprises polymaleic acid polymers.
CN201611149591.4 discloses a water scrubber scale inhibition dispersant and a use method thereof, wherein the dispersant comprises maleic anhydride, and the emulsifier comprises polyoxyethylene sorbitan monooleate.
Disclosure of Invention
In view of the above, the present invention aims to overcome the defects of the prior art and provide an economical and environment-friendly phosphorus-free corrosion and scale inhibitor and a preparation method thereof. The components in the scale inhibitor are simple and easily available in raw materials, mild in preparation conditions, strong in synergistic capability of the components in the scale inhibitor and good in popularization and application values.
In order to achieve the above object, the first aspect of the present invention provides a phosphorus-free corrosion and scale inhibitor, which comprises the following components: sorbitol maleate mixture, zinc chloride, poly dimethyl diallyl ammonium chloride, benzotriazole and the balance of water; the dosage of each component is as follows according to the mass percentage: 30-70% of sorbitol maleate mixture, 2-8% of zinc chloride, 1-5% of poly dimethyl diallyl ammonium chloride, 0.5-3% of benzotriazole and the balance of water, wherein the sum of the components is 100%.
In the present invention, the sorbitol maleate mixture consists of sorbitol maleate monoester, sorbitol maleate diester and sorbitol.
Further, the molar ratio of the maleic acid sorbitol monoester to the maleic acid sorbitol diester to sorbitol is 0.2-0.6: 1: 0.2-0.5. The proportion can enable the three to form an annular stable structure by hydrogen bonds more easily, and the three cooperate with each other to greatly increase the chelating and dispersing capacity to scale ions such as calcium, magnesium and the like; and the scale inhibitor with the annular stable structure can form a film layer on the surface of the metal, so that the scale inhibitor has good corrosion inhibition performance on the metal.
In the invention, the maleic acid sorbitol ester mixture is prepared by the following method: the preparation method comprises the following steps: maleic anhydride and sorbitol are used as raw materials to synthesize a mixture of maleic acid sorbitol monoester, maleic acid sorbitol diester and sorbitol under the catalysis of inorganic acid or inorganic base; or (II) the preparation method II: firstly, preparing methyl maleate from maleic acid and methanol, and then carrying out transesterification reaction on the methyl maleate and sorbitol under the catalysis of inorganic base to obtain maleic acid sorbitol monoester, maleic acid sorbitol diester and sorbitol, thus obtaining the maleic acid sorbitol ester mixture.
Specifically, the first preparation method of the maleic acid sorbitol ester mixture comprises the following steps: adding 100 parts by mass of maleic anhydride, 183-365 parts by mass of sorbitol into a reaction kettle, then adding 1-5 parts by mass of inorganic acid or inorganic base catalyst, heating to 60-80 ℃, stirring for reaction for 0.5-2 hours, then vacuumizing, maintaining the vacuum degree of 70-90 kPa, stopping heating until no water is evaporated, and cooling to obtain light yellow viscous liquid, namely the maleic acid-sorbitol ester mixture.
The sorbitol is industrial sorbitol solid or sorbitol aqueous solution with mass concentration not less than 50%, and when the raw material is industrial sorbitol solid, water with the mass equal to that of maleic anhydride needs to be added to uniformly mix the maleic anhydride and the sorbitol;
the inorganic acid or inorganic base catalyst is preferably concentrated sulfuric acid or potassium carbonate.
Specifically, the second preparation method of the maleic acid sorbitol ester mixture comprises the following steps: adding 100 parts by mass of maleic anhydride and 32-128 parts by mass of methanol into a reaction kettle, heating to 60-80 ℃, carrying out reflux reaction for 1-2 hours, distilling at 70-100 ℃ to remove excessive methanol, adding industrial sorbitol solid containing 185-type 365 parts of sorbitol into the reaction kettle, adding 1-5 parts of potassium carbonate as a catalyst, heating to 80-90 ℃, carrying out stirring reaction for 0.5-2 hours until the methanol is evaporated, stopping heating, cooling to room temperature, adding 30-70 parts of water, and uniformly stirring to obtain light yellow viscous liquid, namely the maleic acid sorbitol ester mixture.
The invention also provides a preparation method of the phosphorus-free corrosion and scale inhibitor, which comprises the following steps: sequentially adding a sorbitol maleate mixture, zinc chloride, poly dimethyl diallyl ammonium chloride, benzotriazole and water in a reaction kettle according to a certain weight part ratio, heating to 45-80 ℃, and stirring for reacting for 0.5 hour to obtain a light yellow liquid, namely the phosphorus-free corrosion and scale inhibitor. The corrosion and scale inhibitor obtained by the invention does not contain any phosphorus-containing compound, the raw materials are easy to obtain, and the product is easy to biodegrade after being discharged; the corrosion and scale inhibitor uses a sorbitol maleate mixture as a main scale inhibiting component, zinc chloride, poly-dimethyl diallyl ammonium chloride and benzotriazole are added to form the phosphorus-free corrosion and scale inhibitor, chelating cations which are easy to form a corrosion inhibition film are provided by the zinc chloride, N in the benzotriazole and the sorbitol maleate mixture can form a stable corrosion inhibition film through hydrogen bond, complexation and the like, the poly-dimethyl diallyl ammonium chloride serving as a cationic surfactant can promote the uniform spreading of the corrosion inhibition film to strengthen the synergistic effect of the components, so that the corrosion inhibition performance of the product is improved, and the poly-dimethyl diallyl ammonium chloride has the sterilization and algae removal performance.
The invention also provides the application of the phosphorus-free corrosion and scale inhibitor in circulating cooling water.
Compared with the prior art, the corrosion and scale inhibitor is prepared by firstly preparing the maleic acid sorbitol ester mixture as the main component of the corrosion and scale inhibitor and then mixing the maleic acid sorbitol ester mixture with zinc chloride, poly dimethyl diallyl ammonium chloride and benzotriazole. The components in the scale inhibitor are easy to obtain, the preparation conditions are mild, and the synergistic capability of the components in the scale inhibitor is strong. Has good popularization and application value.
Detailed Description
The following examples further illustrate embodiments of the present invention.
And (3) testing corrosion and scale inhibition performance: for total hardness (as CaC 0)3Meter) 258mg/L, Cl-Raw water with the content of 95mg/L and the pH value of 7.89 is evaporated and concentrated to Cl in a constant temperature water bath at about 50 DEG C-The content is up to 800-850 mg/L. The concentrated water is used for static scale inhibition test and rotary coupon corrosion test in GBT18175-2000, carbon steel standard coupon, and test piece surface area is 28cm2Standard stainless steel coupon, 28cm surface area of test piece2And a 12-hour sterilization experiment is also carried out, heterotrophic bacteria, sulfate reducing bacteria and iron bacteria are subjected to experiments, and the experimental conditions are as follows: pH is 8.0-9.0, and initial bacterial count: 1.2X 106one/mL.
The dosage of the corrosion and scale inhibitor is 60 mg/L.
The calculation formula of the scale inhibition rate is as follows: the calculation formula of the scale inhibition rate is as follows:
Ca2+ 0- -Ca measured in water before the test2+The concentration of the active carbon is mg/L,
Ca2+ 1- -Ca measured in water after test2+The concentration of the active carbon is mg/L,
Ca2+ 2- -Ca measured after blank (i.e. without addition of water treatment agent) test2+The concentration of the active carbon is mg/L,
the corrosion inhibition rate is calculated according to 8.1 and 8.2 in national standard GBT 18175-2000.
The sterilization rate is calculated according to the change of the number of bacteria before and after the test:
Φ＝(N0-N)/N0×100％
phi is the sterilization rate (%),
N0the number of bacteria (number/L) of raw water before the sterilization treatment,
n is the number of bacteria (number/L) in the effluent after the disinfection treatment.
Example 1
Adding 100 parts by mass of maleic anhydride, 190 parts by mass of sorbitol solid, 100 parts by mass of water and 1 part by mass of concentrated sulfuric acid into a reaction kettle, heating to 65 ℃, stirring for reaction for 2 hours, carrying out reduced pressure distillation, and maintaining the vacuum degree of 70kPa until no water is evaporated to obtain about 350 parts by mass of a maleic acid sorbitol ester mixture;
and adding 60 parts by mass of the mixture into a reaction kettle, adding 30 parts of water, 8 parts of zinc chloride, 1 part of poly dimethyl diallyl ammonium chloride and 0.5 part of benzotriazole under stirring, heating to 50 ℃ for reaction for 1.5 hours, and cooling to obtain the light yellow liquid phosphorus-free corrosion and scale inhibitor. The scale inhibition rate, the corrosion inhibition rate and the sterilization rate obtained by the testing method are respectively 97.8%, 91.6% and 18%.
Example 2
Adding 100 parts by mass of maleic anhydride, 365 parts by mass of sorbitol solid, 100 parts by mass of water and 1 part by mass of concentrated sulfuric acid into a reaction kettle, heating to 80 ℃, stirring for reaction for 1.5 hours, carrying out reduced pressure distillation, and maintaining the vacuum degree of 90kPa until no water is evaporated to obtain about 510 parts by mass of a maleic acid sorbitol ester mixture;
adding 50 parts by mass of the mixture into a reaction kettle, adding 40 parts of water, 2 parts of zinc chloride, 2 parts of poly dimethyl diallyl ammonium chloride and 0.5 part of benzotriazole under stirring, heating to 45 ℃ for reaction for 2 hours, and cooling to obtain the light yellow liquid phosphorus-free corrosion and scale inhibitor. The scale inhibition rate is 98.9%, the corrosion inhibition rate is 91.2%, and the sterilization rate is 24% according to the test method.
Example 3
Adding 100 parts by mass of maleic anhydride, 272 parts by mass of sorbitol aqueous solution (the sorbitol content is 190 parts) and 5 parts by mass of potassium carbonate into a reaction kettle, heating to 65 ℃, stirring for reaction for 1 hour, carrying out reduced pressure distillation, and maintaining the vacuum degree of 70kPa until no moisture is evaporated to obtain about 350 parts by mass of a maleic acid sorbitol ester mixture;
adding 65 parts by mass of the mixture into a reaction kettle, adding 25 parts of water, 6 parts of zinc chloride, 2 parts of poly dimethyl diallyl ammonium chloride and 1 part of benzotriazole under stirring, heating to 55 ℃, reacting for 1 hour, and cooling to obtain the light yellow liquid phosphorus-free corrosion and scale inhibitor. The scale inhibition rate, the corrosion inhibition rate and the sterilization rate obtained by the test method are respectively 97.9%, 92.1% and 28%.
Example 4
Heating 100 parts by mass of maleic anhydride and 40 parts by mass of methanol to 60 ℃ for reflux reaction for 2 hours, distilling at 80 ℃ to remove excessive methanol, adding 200 parts by mass of sorbitol solid and 5 parts by mass of potassium carbonate into a reaction kettle, heating to 80-90 ℃, stirring for reaction for 1 hour, distilling until no methanol is evaporated, cooling, adding 50 parts by mass of water, and uniformly stirring to obtain about 320 parts by mass of a sorbitol maleate mixture;
and adding 70 parts by mass of the mixture into a reaction kettle, adding 20 parts of water, 4 parts of zinc chloride, 3 parts of poly dimethyl diallyl ammonium chloride and 1 part of benzotriazole under stirring, heating to 55 ℃, reacting for 1 hour, and cooling to obtain the light yellow liquid phosphorus-free corrosion and scale inhibitor. The scale inhibition rate is 97.2%, the corrosion inhibition rate is 90.7%, and the sterilization rate is 32% according to the test method.
Comparative example 1
Adding 50 parts by mass of maleic acid sorbitol monoester into a reaction kettle, adding 40 parts of water, 2 parts of zinc chloride, 2 parts of poly dimethyl diallyl ammonium chloride and 0.5 part of benzotriazole under stirring, heating to 45 ℃, reacting for 2 hours, and cooling to obtain the light yellow liquid phosphorus-free corrosion and scale inhibitor. The scale inhibition rate obtained by the test method is 78.9 percent, and the corrosion inhibition rate is 87.2 percent. The sterilization rate is 28 percent.
Comparative example 2
Adding 50 parts by mass of sorbitol maleate diester and sorbitol into a reaction kettle, adding 40 parts of water, 2 parts of zinc chloride, 2 parts of poly (dimethyl diallyl ammonium chloride) and 0.5 part of benzotriazole into the reaction kettle while stirring, heating the mixture to 45 ℃ for reacting for 2 hours, and cooling the mixture to obtain the light yellow liquid phosphorus-free corrosion and scale inhibitor. The scale inhibition rate obtained by the test method is 88.5 percent, and the corrosion inhibition rate is 89.1 percent. The sterilization rate is 27%.
Claims (8)
1. A phosphorus-free corrosion and scale inhibitor is characterized by comprising the following components: sorbitol maleate mixture, zinc chloride, poly dimethyl diallyl ammonium chloride, benzotriazole and the balance of water; the dosage of each component is as follows according to the mass percentage: 30-70% of a maleic acid sorbitol ester mixture, 2-8% of zinc chloride, 1-5% of poly dimethyl diallyl ammonium chloride, 0.5-3% of benzotriazole and the balance of water, wherein the sum of the components is 100%;
the sorbitol maleate mixture consists of sorbitol maleate monoester, sorbitol maleate diester and sorbitol.
2. The phosphorus-free corrosion and scale inhibitor according to claim 1, wherein the molar ratio of the sorbitol maleate monoester to the sorbitol maleate diester to the sorbitol is 0.2-0.6: 1: 0.2-0.5.
3. The phosphorus-free corrosion and scale inhibitor according to claim 1 or 2, wherein the sorbitol maleate mixture is prepared by the following method: the preparation method comprises the following steps: maleic anhydride and sorbitol are used as raw materials to synthesize a mixture of maleic acid sorbitol monoester, maleic acid sorbitol diester and sorbitol under the catalysis of inorganic acid or inorganic base; or the preparation method II comprises the following steps: firstly, preparing methyl maleate from maleic acid and methanol, and then carrying out transesterification reaction on the methyl maleate and sorbitol under the catalysis of inorganic base to obtain maleic acid sorbitol monoester, maleic acid sorbitol diester and sorbitol, thus obtaining the maleic acid sorbitol ester mixture.
4. The phosphorus-free corrosion and scale inhibitor according to claim 3, wherein the first preparation method of the sorbitol maleate mixture comprises: adding 100 parts by mass of maleic anhydride and 183-365 parts by mass of sorbitol into a reaction kettle, uniformly mixing, then adding 1-5 parts by mass of an inorganic acid or inorganic base catalyst, heating to 60-80 ℃, stirring for reaction for 0.5-2 hours, then vacuumizing, maintaining the vacuum degree of 70-90 kPa, stopping heating until no water is evaporated, and cooling to obtain a light yellow viscous liquid, namely a maleic acid sorbitol ester mixture.
5. The phosphorus-free corrosion and scale inhibitor according to claim 4, wherein sorbitol is industrial sorbitol solid or a sorbitol aqueous solution with a mass concentration of not less than 50%, and when the raw material is industrial sorbitol solid, water with the mass of maleic anhydride and the like is added to uniformly mix maleic anhydride and sorbitol;
the inorganic acid or inorganic base catalyst is concentrated sulfuric acid or potassium carbonate.
6. The phosphorus-free corrosion and scale inhibitor according to claim 3, wherein the second preparation method of the sorbitol maleate mixture comprises the following steps: adding 100 parts by mass of maleic anhydride and 32-128 parts by mass of methanol into a reaction kettle, heating to 60-80 ℃, carrying out reflux reaction for 1-2 hours, distilling at 70-100 ℃ to remove excessive methanol, adding industrial sorbitol solid containing 185-type 365 parts of sorbitol into the reaction kettle, adding 1-5 parts of potassium carbonate as a catalyst, heating to 80-90 ℃, carrying out stirring reaction for 0.5-2 hours until the methanol is evaporated, stopping heating, cooling to room temperature, adding 30-70 parts of water, and uniformly stirring to obtain light yellow viscous liquid, namely the maleic acid sorbitol ester mixture.
7. The method for preparing the phosphorus-free corrosion and scale inhibitor of any one of claims 1 to 6, which is characterized by comprising the following steps: sequentially adding a sorbitol maleate mixture, zinc chloride, poly dimethyl diallyl ammonium chloride, benzotriazole and water in a reaction kettle according to a certain weight part ratio, heating to 45-80 ℃, and stirring for reacting for 0.5 hour to obtain a light yellow liquid, namely the phosphorus-free corrosion and scale inhibitor.
8. Use of the phosphorus-free corrosion and scale inhibitor of any one of claims 1-6 in circulating cooling water.
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| EP0122013A1 (en) * | 1983-03-07 | 1984-10-17 | Calgon Corporation | Polymeric additives for water |
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