CN110862495A - Multifunctional phosphorus-free corrosion and scale inhibitor based on humic acid derivatives and preparation method thereof - Google Patents
Multifunctional phosphorus-free corrosion and scale inhibitor based on humic acid derivatives and preparation method thereof Download PDFInfo
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- CN110862495A CN110862495A CN201911099631.2A CN201911099631A CN110862495A CN 110862495 A CN110862495 A CN 110862495A CN 201911099631 A CN201911099631 A CN 201911099631A CN 110862495 A CN110862495 A CN 110862495A
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- humic acid
- scale inhibitor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
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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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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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 discloses a multifunctional phosphorus-free corrosion and scale inhibitor based on humic acid derivatives and a preparation method thereof. The synthesized polymethacrylate humic acid ester is a new corrosion and scale inhibitor single agent, the molecular structure contains a large amount of hydroxyl and carboxyl, the straight chain and the branched chain extend alternately, and the molecular weight can be regulated and controlled through the formula design; the corrosion and scale inhibitor disclosed by the invention is phosphorus-free, nitrogen-free and zinc-free, can realize zero-pollution discharge operation, has a good corrosion and scale inhibition effect when being used in a circulating cooling water system, is an environment-friendly corrosion and scale inhibitor, and has a flocculation effect.
Description
Technical Field
The invention relates to the field of corrosion and scale inhibitors, in particular to a multifunctional phosphorus-free corrosion and scale inhibitor based on humic acid derivatives and a preparation method thereof.
Background
The cooling water consumption in the current industrial water accounts for a large proportion, the supply condition of the cooling water plays an important role in the operation of the whole enterprise, and the reuse rate of the cooling water is improved as much as possible to save the industrial water. However, as the cooling water is continuously evaporated, the salts in the water are concentrated, and the cooling water is in contact with the atmosphere, the content of dissolved oxygen and bacteria is increased, so that the circulating cooling water has serious scaling and corrosion problems, the heat exchange rate is reduced, the maintenance is frequent, and the normal production is threatened. Therefore, it is necessary to add a chemical agent mainly comprising a scale inhibitor and a corrosion inhibitor to the cooling water to solve these problems. In recent years, the application development of the organic phosphoric acid corrosion and scale inhibitor is extremely rapid, and the common corrosion and scale inhibitors for domestic circulating cooling water treatment comprise polyphosphate, phosphoric acid vinegar, organic phosphoric acid, polymers and the like. The organic phosphoric acid medicament is widely applied by the double functions of high-efficiency corrosion inhibition and scale inhibition, and the water treatment medicament has the characteristics of stable chemical performance, high temperature and value resistance, obvious solution limit effect and synergistic effect and the like. However, phosphorus is a nutrient source of bacteria and algae, and the phosphorus-containing scale inhibitor is easy to cause eutrophication of environmental water areas and promote the growth of bacteria and algae to form red tide to cause water source pollution. Therefore, the development of a novel green corrosion and scale inhibitor which is phosphorus-free, has good biodegradation performance, simple and easily realized control index and is suitable for high-concentration-ratio operation and even zero pollution discharge has become a development direction of water treatment.
The patent application No. 200410073666.6 discloses a low-phosphorus composite scale and corrosion inhibitor and application thereof in water treatment, and discloses a low-phosphorus scale and corrosion inhibitor compounded by PBTCA/HPAA, polyaspartic acid and polycarboxylic acid, which has low consumption in circulating cooling water treatment, excellent calcium carbonate scaling resistance function and good corrosion inhibition function. Patent application No. 201510648500.0 "an environment-friendly oilfield reinjection water corrosion and scale inhibitor and its preparation", discloses a method for preparing the corrosion and scale inhibitor by using Erycibe obtusifolia extract, methyl dihydroartemisinin, citric acid, tannic acid, sodium mercaptobenzothiazole, gluconic acid-delta-lactone, potassium guaiacolsulfonate, sulfosuccinate, N- (3-ethoxysilylpropyl) glucamide, ethyl acetate, ethanol and water as raw materials. Meanwhile, the patent indicates that the corrosion inhibition rate and the scale inhibition rate both reach more than 95 percent. Patent application No. 201410731750.6, "a method for preparing a phosphorus-free corrosion and scale inhibitor", discloses that the main components are polyepoxysuccinic acid sodium, carbon steel corrosion inhibitor, surfactant, reinforcing agent, etc., but the information of some medicaments is incomplete. In addition to the above-mentioned related patents, there are many patents disclosing corrosion and scale inhibitors, but most of them are based on application background to make formulation design, and then make them implement improvement of product performance by means of compounding.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel corrosion and scale inhibitor single agent which is environment-friendly and has good corrosion and scale inhibition and flocculation effects aiming at the defects of the prior art.
In order to solve the technical problems, the invention discloses a multifunctional phosphorus-free corrosion and scale inhibitor based on humic acid derivatives, which is prepared by taking humic acid and methacrylic acid as raw materials, synthesizing polymethacrylate through polymerization and esterification of free radicals under the action of a catalyst and an initiator, and then mixing the polymethacrylate with a synergistic reactant and a solvent.
Specifically, the catalyst used for synthesizing the polymethacrylate humate is p-toluenesulfonic acid; the initiator is azobisisobutyronitrile;
wherein the mass fraction of each reaction raw material is as follows:
humic acid accounts for 15-60% of the total mass of the reaction raw materials;
methacrylic acid accounts for 10-45% of the total mass of the reaction raw materials;
the catalyst p-toluenesulfonic acid accounts for 0.2-3% of the total mass of the reaction raw materials;
the initiator azobisisobutyronitrile accounts for 0.1-1% of the total mass of the reaction raw materials;
the balance being solvent xylene.
Specifically, the synergistic agent is thiourea and potassium iodide; a mixed solvent of the solvent and methanol and water;
wherein the mass fraction of each component is as follows:
20-60% of polymethacrylate humate;
1-15% of thiourea;
1-20% of potassium iodide;
20-50% of methanol;
the balance of deionized water.
The invention further provides a preparation method of the multifunctional phosphorus-free corrosion and scale inhibitor based on the humic acid derivative, which comprises the following steps:
(1) adding humic acid, methacrylic acid, a catalyst and an initiator into a proper solvent, stirring and mixing, and controlling the temperature to perform polymerization and esterification reaction on free radicals; then, decompressing and steaming out the solvent in the reaction system to obtain the polymethacrylic acid humic acid ester;
(2) and (2) mixing the polymethacrylate humic acid ester obtained in the step (1) with the synergistic agent and the solvent, and uniformly stirring to obtain the compound.
Specifically, in the step (1), the temperature for polymerizing the free radicals is 40-80 ℃, and the polymethacrylic acid is prepared.
Specifically, in the step (1), the temperature of the esterification reaction is 120-150 ℃, and the polymethacrylate humate is prepared.
Has the advantages that:
1. the synthesized polymethacrylate humic acid ester is a new corrosion and scale inhibitor single agent, the molecular structure contains a large amount of hydroxyl and carboxyl, the linear chain and the branched chain are alternately extended, and the molecular weight can be regulated and controlled through the formula design.
2. The corrosion and scale inhibitor disclosed by the invention is free of phosphorus, nitrogen and zinc, can realize zero-pollution discharge operation, has good corrosion and scale inhibition effects when being used in a circulating cooling water system, is an environment-friendly corrosion and scale inhibitor, and has a flocculation effect.
Detailed Description
The invention will be better understood from the following examples.
Example 1
Adding 15 g of humic acid, 25 g of methacrylic acid, 1 g of p-toluenesulfonic acid and 0.5 g of azobisisobutyronitrile into 59 g of dimethylbenzene, stirring and mixing, controlling the temperature at 65 ℃ to enable the methacrylic acid to generate polymerization reaction and partial esterification reaction at 130 ℃, and finishing the reaction when the separated water amount is about 3.5 g. Then, the solvent in the reaction system is distilled out under reduced pressure at 85 ℃ and-0.2 MPa to obtain the polyacrylic acid humic acid ester.
Mixing 40 g of polymethacrylate humic acid ester, 2 g of thiourea, 10 g of potassium iodide, 20 g of methanol, 38 g of water and the like, and uniformly stirring to obtain the target product of the patent.
Example 2
Adding 25 g of humic acid, 20 g of methacrylic acid, 2 g of p-toluenesulfonic acid and 1 g of azobisisobutyronitrile into 50 g of dimethylbenzene, stirring and mixing, controlling the temperature to be 75 ℃ to enable the methacrylic acid to generate polymerization reaction, controlling the temperature to be 140 ℃ to enable the humic acid to generate partial esterification reaction, and finishing the reaction when the separated water amount is about 3 g. Then, the solvent in the reaction system is distilled out under reduced pressure at 85 ℃ and-0.2 MPa to obtain the polymethacrylic acid humate.
Mixing 45 g of polymethacrylic acid humic acid ester, 5 g of thiourea, 8 g of potassium iodide, 25 g of methanol, 17 g of water and the like, and uniformly stirring to obtain the target product of the patent.
Example 3
The scale inhibition rate and corrosion inhibition rate of examples 1 and 2 were measured, and the results are shown in table 1.
Wherein the scale inhibition rate is measured according to the execution standard Q/SY 126-2014; the method for determining the corrosion inhibition rate is in accordance with the implementation Standard Q/SY 126-2014.
TABLE 1
| Serial number | Name (R) | The scale inhibition rate% | Corrosion inhibition rate% |
| 1 | Example 1 product | 95 | 90 |
| 2 | EXAMPLE 2 product | 94 | 88 |
As can be seen from the data in table 1: the scale inhibition rate and the corrosion inhibition rate of the corrosion and scale inhibitor obtained by the invention are both higher than the standard requirements, the corrosion and scale inhibitor has better scale inhibition and corrosion inhibition effects, and the components of the corrosion and scale inhibitor are free of phosphine compounds, so that the corrosion and scale inhibitor conforms to the development concept of environmental protection.
The invention provides a multifunctional phosphorus-free corrosion and scale inhibitor based on humic acid derivatives and a preparation method thereof, and particularly provides a plurality of methods and ways for realizing the technical scheme. All the components not specified in the present embodiment can be realized by the prior art.
Claims (6)
1. A multifunctional phosphorus-free corrosion and scale inhibitor based on humic acid derivatives is characterized in that humic acid and methacrylic acid are used as raw materials, poly (methyl methacrylate) humic acid ester is synthesized through polymerization and esterification of free radicals under the action of a catalyst and an initiator, and then the poly (methyl methacrylate) humic acid ester is mixed with a synergistic reactant and a solvent to prepare the phosphorus-free corrosion and scale inhibitor.
2. The multifunctional humic acid derivative-based phosphorus-free corrosion and scale inhibitor according to claim 1, wherein the catalyst used for synthesizing the polymethacrylic acid humate is p-toluenesulfonic acid; the initiator is azobisisobutyronitrile;
wherein the mass fraction of each reaction raw material is as follows:
humic acid accounts for 14-30% of the total mass of the reaction raw materials;
methacrylic acid accounts for 20-25% of the total mass of the reaction raw materials;
the catalyst p-toluenesulfonic acid accounts for 0.9-3% of the total mass of the reaction raw materials;
the initiator azobisisobutyronitrile accounts for 0.4-1.5% of the total mass of the reaction raw materials;
the balance being solvent xylene.
3. The multifunctional humic acid derivative-based phosphorus-free corrosion and scale inhibitor according to claim 1, wherein the synergistic agent is thiourea and potassium iodide; a mixed solvent of the solvent and methanol and water;
wherein the mass fraction of each component is as follows:
36-45% of polymethacrylate humate;
1.5 to 5 percent of thiourea;
8-10% of potassium iodide;
18-25% of methanol;
the balance of deionized water.
4. The preparation method of the multifunctional phosphorus-free corrosion and scale inhibitor based on the humic acid derivative as claimed in claim 1 is characterized by comprising the following steps:
(1) adding humic acid, methacrylic acid, a catalyst and an initiator into a proper solvent, stirring and mixing, and controlling the temperature to perform polymerization and esterification reaction on free radicals; then, decompressing and steaming out the solvent in the reaction system to obtain the polymethacrylic acid humic acid ester;
(2) and (2) mixing the polymethacrylate humic acid ester obtained in the step (1) with the synergistic agent and the solvent, and uniformly stirring to obtain the compound.
5. The method for preparing the multifunctional humic acid derivative-based phosphorus-free corrosion and scale inhibitor according to claim 4, wherein in the step (1), the temperature for polymerizing the free radicals is 40-80 ℃.
6. The method for preparing the multifunctional humic acid derivative-based phosphorus-free corrosion and scale inhibitor as claimed in claim 4, wherein the esterification reaction temperature in step (1) is 120-150 ℃.
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| CN112093918A (en) * | 2020-08-31 | 2020-12-18 | 中化化工科学技术研究总院有限公司 | Humic acid phosphorus-free corrosion and scale inhibitor and preparation method thereof |
| CN112624355A (en) * | 2020-12-22 | 2021-04-09 | 句容宁武高新技术发展有限公司 | Multifunctional green group-rich corrosion and scale inhibitor and preparation method thereof |
| CN114180730A (en) * | 2021-11-19 | 2022-03-15 | 铜陵晟泽环保科技有限公司 | High-concentration multiple corrosion and scale inhibitor for circulating cooling water system and water treatment method |
| CN115785474A (en) * | 2022-12-20 | 2023-03-14 | 山东鑫泰水处理技术股份有限公司 | Isothioureido-terminated pentaerythritol core dendritic polymer, and preparation method and corrosion inhibition application thereof |
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| CN112624355A (en) * | 2020-12-22 | 2021-04-09 | 句容宁武高新技术发展有限公司 | Multifunctional green group-rich corrosion and scale inhibitor and preparation method thereof |
| CN114180730A (en) * | 2021-11-19 | 2022-03-15 | 铜陵晟泽环保科技有限公司 | High-concentration multiple corrosion and scale inhibitor for circulating cooling water system and water treatment method |
| CN115785474A (en) * | 2022-12-20 | 2023-03-14 | 山东鑫泰水处理技术股份有限公司 | Isothioureido-terminated pentaerythritol core dendritic polymer, and preparation method and corrosion inhibition application thereof |
| CN115785474B (en) * | 2022-12-20 | 2023-08-25 | 山东鑫泰水处理技术股份有限公司 | Thiosemicarbazide-terminated pentaerythritol core dendritic polymer and preparation method and corrosion inhibition application thereof |
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Application publication date: 20200306 |