CN112626510A - Efficient environment-friendly pre-filming agent - Google Patents
Efficient environment-friendly pre-filming agent Download PDFInfo
- Publication number
- CN112626510A CN112626510A CN202011471804.1A CN202011471804A CN112626510A CN 112626510 A CN112626510 A CN 112626510A CN 202011471804 A CN202011471804 A CN 202011471804A CN 112626510 A CN112626510 A CN 112626510A
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- Prior art keywords
- percent
- filming
- water
- friendly
- acrylate
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 16
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012964 benzotriazole Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000012207 sodium gluconate Nutrition 0.000 claims abstract description 11
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 11
- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 8
- 239000011592 zinc chloride Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 3
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- 239000011574 phosphorus Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 238000012851 eutrophication Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000000498 cooling water Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
Abstract
The invention discloses a high-efficiency environment-friendly pre-film agent, which comprises the following components in percentage by mass: 20 to 40 percent of acrylic acid-acrylate-sulfonate copolymer, 1 to 10 percent of sodium gluconate, 2 to 10 percent of zinc salt, 0.5 to 3 percent of benzotriazole, 0.5 to 3 percent of concentrated sulfuric acid and the balance of water; wherein the solid content of the acrylic acid-acrylate-sulfonate copolymer is not less than 25.0%, and the number average molecular weight is 2000-15000; the zinc salt is one or two mixtures of zinc chloride or zinc sulfate. The pre-filming agent disclosed by the invention is free from phosphorus, does not cause eutrophication to water quality in use, does not need to add acid to adjust the acidity of a solution in the pre-filming of an industrial circulating water system, has an obvious pre-filming effect, greatly shortens the pre-filming time, does not need to carry out system replacement and water quality discharge after pre-filming, can be directly converted into normal operation of the system, saves water resources and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of industrial circulating cooling water treatment, and particularly relates to a phosphorus-free pre-filming treatment technology for an industrial circulating cooling water system.
Background
An industrial circulating cooling water system needs to be cleaned and pre-filmed before a new system is operated, and an old system needs to be cleaned and pre-filmed in time. A layer of compact protective film can be formed on the surface of the metal after pre-filming, so that the corrosion rate can be effectively reduced, the service lives of the pipeline and the heat exchanger are prolonged, and the normal operation of the system is guaranteed.
At present, phosphate is used as a pre-film agent for most industrial circulating water treatment, the phosphorus content of the formula is high, the problems of water pollution and water eutrophication exist, and the standard of environmental protection and direct discharge cannot be met. Particularly, in recent years, the problem of water eutrophication is becoming more serious, phosphorus is a nutrient source of microorganisms, the influence on the environment is becoming more severe, and phosphorus-free water treatment agents are gradually becoming the development trend in the future. Therefore, the research of the phosphorus-free medicament has important significance.
Disclosure of Invention
The invention aims to provide an efficient and environment-friendly phosphorus-free prefilming agent which does not contain phosphorus and bring eutrophication harm to water, has a good prefilming effect and can form a stable adsorption film on the metal surface of equipment.
Aiming at the purposes, the high-efficiency environment-friendly pre-filming agent adopted by the invention comprises the following components in percentage by mass: 20 to 40 percent of acrylic acid-acrylate-sulfonate copolymer, 1 to 10 percent of sodium gluconate, 2 to 10 percent of zinc salt, 0.5 to 3 percent of benzotriazole, 0.5 to 3 percent of concentrated sulfuric acid and the balance of water.
The invention further preferably selects the mass percentage composition of the pre-filming agent as follows: 25-35% of acrylic acid-acrylate-sulfonate copolymer, 2-7% of sodium gluconate, 5-7% of zinc salt, 1-2% of benzotriazole, 1-2% of concentrated sulfuric acid and the balance of water.
The solid content of the acrylic acid-acrylate-sulfonate copolymer is more than or equal to 25.0 percent, and the number average molecular weight of the acrylic acid-acrylate-sulfonate copolymer is 2000-15000.
The sodium gluconate is a commercial industrial product with the concentration of 98 percent.
The zinc salt is one or two of zinc chloride or zinc sulfate.
The benzotriazole is a commercial industrial product, and the content of the benzotriazole is 99 percent.
The concentrated sulfuric acid is an industrial product with the content of 95-98 percent.
The invention has the following beneficial effects:
the pre-filming agent does not contain phosphorus, and does not cause eutrophication to water quality when in use; when carbon steel is subjected to pre-filming, the pre-filming effect is good and is higher than 10s specified in HG/T3778 (the determination time of copper sulfate is more than 30 s); when the industrial circulating water system is pre-filmed, the acidity of the solution is not required to be adjusted by adding acid; the system replacement and water quality discharge are not needed after the pre-filming, and the normal operation of the system can be directly converted, so that the water resource is saved, and the environment is protected; when trace benzotriazole is added, the pre-filming effect is obvious, and the pre-filming time is greatly shortened.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
The solid content of the acrylic acid-acrylate-sulfonate copolymer used in the following examples is not less than 25.0%, and the number average molecular weight is 2000-15000; sodium gluconate is a commercial industrial product with the concentration of 98 percent; the purity of the zinc chloride is 98 percent; benzotriazole is a commercial industrial product with the content of 99 percent; concentrated sulfuric acid is an industrial product with the content of 95-98 percent.
Example 1
Adding 250g of acrylic acid-acrylate-sulfonate copolymer, 20g of sodium gluconate, 70g of zinc chloride, 15g of benzotriazole and 5g of concentrated sulfuric acid into 640g of water in sequence, and uniformly stirring to obtain the pre-film agent.
Example 2
Adding 280g of acrylic acid-acrylate-sulfonate copolymer, 50g of sodium gluconate, 50g of zinc chloride, 20g of benzotriazole and 10g of concentrated sulfuric acid into 590g of water in sequence, and uniformly stirring to obtain the prefilming agent.
Embodiment 3
Adding 300g of acrylic acid-acrylate-sulfonate copolymer, 70g of sodium gluconate, 60g of zinc chloride, 5g of benzotriazole and 15g of concentrated sulfuric acid into 550g of water in sequence, and uniformly stirring to obtain the pre-film agent.
Example 4
350g of acrylic acid-acrylate-sulfonate copolymer, 20g of sodium gluconate, 50g of zinc chloride, 20g of benzotriazole and 20g of concentrated sulfuric acid are sequentially added into 540g of water and stirred uniformly to obtain the prefilming agent.
The quality indexes of the pre-film agents prepared in the embodiments 1-4 are checked, the appearance of the pre-film agents is light yellow transparent liquid, the density (25 ℃) is more than or equal to 1.050, the pH (1% aqueous solution) is 2-5, and the total phosphorus (in PO) is used4 3-Calculated), the solid content is more than or equal to 35.0 percent.
The pre-film agents prepared in examples 1 to 4 were subjected to a pre-film test, and compared with a laboratory pre-film test without benzotriazole (replaced with equal mass of water), the results are shown in table 1.
TABLE 1
Note: in the table, the corrosion resistance time of the membrane is the time when the surface of the membrane turns red by titration with a copper sulfate standard solution.
As can be seen from the experimental data in Table 1, after benzotriazole is added into the prefilming agent, the prefilming agent has a synergistic effect on the film forming effect and has a remarkable effect.
In order to further prove the pre-filming effect of the pre-filming agent, the pre-filming agent prepared in the above examples 1 to 4 was compared with the high-efficiency non-phosphorus pre-filming agent invented by the people of the treet (treet, zhao ming xi, liukun, etc.; the high-efficiency non-phosphorus pre-filming agent XT-0631 performance effect, 2016 chinese water treatment technical seminar and the 36 th annual meeting argument) and the high-efficiency non-phosphorus pre-filming agent invented by the people of the qiuhua, wangming, tests and field application of the circulating cooling water non-phosphorus pre-filming agent, industrial water treatment) and the results are shown in table 2.
TABLE 2
| Medicament | Dosage (mg/L) | Hanging sheet material | Corrosion resistance time(s) of film |
| Example 1 | 300 | 20# | 145 |
| Example 2 | 300 | 20# | 150 |
| Example 3 | 300 | 20# | 137 |
| Example 4 | 300 | 20# | 132 |
| Non-phosphate prefilming agent (Jing jin) | 300 | 20# | 120 |
| Non-phosphate prefilming agent (Qiuhua) | 300 | 20# | 21 |
Note: in the table, the corrosion resistance time of the membrane is the time when the surface of the membrane turns red by titration with a copper sulfate standard solution.
As can be seen from Table 2, compared with other phosphorus-free medicaments, the film-forming corrosion-resistant time of the prefilming agent is longer, is far higher than 10s specified by HG/T3778, is also far higher than that of the conventional phosphorus-free medicament, has good film-forming effect, and can be used for prefilming an on-site industrial circulating water system.
Claims (4)
1. The efficient environment-friendly pre-film agent is characterized by comprising the following components in percentage by mass: 20 to 40 percent of acrylic acid-acrylate-sulfonate copolymer, 1 to 10 percent of sodium gluconate, 2 to 10 percent of zinc salt, 0.5 to 3 percent of benzotriazole, 0.5 to 3 percent of concentrated sulfuric acid and the balance of water.
2. The efficient environment-friendly prefilming agent as claimed in claim 1, wherein the prefilming agent comprises the following components by mass percent: 25-35% of acrylic acid-acrylate-sulfonate copolymer, 2-7% of sodium gluconate, 5-7% of zinc salt, 1-2% of benzotriazole, 1-2% of concentrated sulfuric acid and the balance of water.
3. The high-efficiency environment-friendly prefilming agent as claimed in claim 1 or 2, which is characterized in that: the acrylic acid-acrylate-sulfonate copolymer has a number average molecular weight of 2000-15000.
4. The high-efficiency environment-friendly prefilming agent as claimed in claim 1 or 2, which is characterized in that: the zinc salt is one or two mixtures of zinc chloride or zinc sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011471804.1A CN112626510A (en) | 2020-12-14 | 2020-12-14 | Efficient environment-friendly pre-filming agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011471804.1A CN112626510A (en) | 2020-12-14 | 2020-12-14 | Efficient environment-friendly pre-filming agent |
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| Publication Number | Publication Date |
|---|---|
| CN112626510A true CN112626510A (en) | 2021-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202011471804.1A Pending CN112626510A (en) | 2020-12-14 | 2020-12-14 | Efficient environment-friendly pre-filming agent |
Country Status (1)
| Country | Link |
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| CN (1) | CN112626510A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115094406A (en) * | 2022-06-20 | 2022-09-23 | 邢台旭阳科技有限公司 | Non-phosphorus prefilming agent and its preparation method and application |
| CN115449783A (en) * | 2022-09-21 | 2022-12-09 | 岳阳隆兴实业有限公司 | Circulating water phosphorus-free prefilming agent and use method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079584A (en) * | 2010-12-14 | 2011-06-01 | 成都齐达水处理工程股份有限公司 | Non-phosphorus scale and corrosion inhibitor, and preparation method and applications thereof |
| CN105174498A (en) * | 2015-07-13 | 2015-12-23 | 鞍钢贝克吉利尼水处理有限公司 | Composite efficient low-phosphorus corrosion-inhibiting and scale-inhibiting agent for low hardness water, and preparation method thereof |
| CN106283012A (en) * | 2016-08-31 | 2017-01-04 | 威海翔宇环保科技股份有限公司 | A kind of recirculated water Phosphateless environmentally friendly prefilming agent |
| CN106702367A (en) * | 2016-12-13 | 2017-05-24 | 崔进 | Efficient non-phosphorus prefilming agent |
| CN111471988A (en) * | 2020-05-22 | 2020-07-31 | 德蓝水技术股份有限公司 | Prefilming agent and preparation method thereof |
-
2020
- 2020-12-14 CN CN202011471804.1A patent/CN112626510A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079584A (en) * | 2010-12-14 | 2011-06-01 | 成都齐达水处理工程股份有限公司 | Non-phosphorus scale and corrosion inhibitor, and preparation method and applications thereof |
| CN105174498A (en) * | 2015-07-13 | 2015-12-23 | 鞍钢贝克吉利尼水处理有限公司 | Composite efficient low-phosphorus corrosion-inhibiting and scale-inhibiting agent for low hardness water, and preparation method thereof |
| CN106283012A (en) * | 2016-08-31 | 2017-01-04 | 威海翔宇环保科技股份有限公司 | A kind of recirculated water Phosphateless environmentally friendly prefilming agent |
| CN106702367A (en) * | 2016-12-13 | 2017-05-24 | 崔进 | Efficient non-phosphorus prefilming agent |
| CN111471988A (en) * | 2020-05-22 | 2020-07-31 | 德蓝水技术股份有限公司 | Prefilming agent and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115094406A (en) * | 2022-06-20 | 2022-09-23 | 邢台旭阳科技有限公司 | Non-phosphorus prefilming agent and its preparation method and application |
| CN115094406B (en) * | 2022-06-20 | 2023-10-20 | 邢台旭阳科技有限公司 | Phosphorus-free prefilming agent and preparation method and application thereof |
| CN115449783A (en) * | 2022-09-21 | 2022-12-09 | 岳阳隆兴实业有限公司 | Circulating water phosphorus-free prefilming agent and use method thereof |
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Application publication date: 20210409 |
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