CN112811614A - Circulating water phosphorus-free scale inhibitor and preparation method thereof - Google Patents
Circulating water phosphorus-free scale inhibitor and preparation method thereof Download PDFInfo
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- CN112811614A CN112811614A CN202011405705.3A CN202011405705A CN112811614A CN 112811614 A CN112811614 A CN 112811614A CN 202011405705 A CN202011405705 A CN 202011405705A CN 112811614 A CN112811614 A CN 112811614A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims description 14
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920001577 copolymer Polymers 0.000 claims abstract description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000003751 zinc Chemical class 0.000 claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims abstract description 27
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 26
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 26
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 54
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 46
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 35
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 23
- 239000011591 potassium Substances 0.000 claims description 23
- 229910052700 potassium Inorganic materials 0.000 claims description 23
- 239000011592 zinc chloride Substances 0.000 claims description 23
- 235000005074 zinc chloride Nutrition 0.000 claims description 23
- 239000011684 sodium molybdate Substances 0.000 claims description 20
- 235000015393 sodium molybdate Nutrition 0.000 claims description 20
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 230000005764 inhibitory process Effects 0.000 abstract description 49
- 230000007797 corrosion Effects 0.000 abstract description 27
- 238000005260 corrosion Methods 0.000 abstract description 27
- 229910000975 Carbon steel Inorganic materials 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010962 carbon steel Substances 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 239000010935 stainless steel Substances 0.000 abstract description 5
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 239000000391 magnesium silicate Substances 0.000 description 6
- 229910052919 magnesium silicate Inorganic materials 0.000 description 6
- 235000019792 magnesium silicate Nutrition 0.000 description 6
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000000378 calcium silicate Substances 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- 102100035024 Carboxypeptidase B Human genes 0.000 description 1
- 101000946524 Homo sapiens Carboxypeptidase B Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000668 effect on calcium Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention provides a circulating water phosphorus-free scale inhibitor which is prepared from the following raw materials in parts by weight: 22-28 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, 3.5-4.5 parts of acrylic acid-2-methylpropanesulfonic acid copolymer, 1.25-1.45 parts of 2-carboxylic acid thiomorpholine, 8-11.5 parts of zinc salt, 23-28 parts of polymaleic anhydride, 1.75-2.15 parts of hydrochloric acid, 13-16.5 parts of polyaspartic acid, 2.7-3.2 parts of molybdate and 16-24 parts of deionized water. The circulating water phosphorus-free scale inhibitor has excellent scale inhibition performance and low corrosion rate, can effectively reduce the corrosion of carbon steel, copper and stainless steel, and is a high-efficiency corrosion and scale inhibitor.
Description
Technical Field
The invention relates to the field of scale inhibitors, in particular to a circulating water non-phosphorus scale inhibitor and a preparation method thereof.
Background
The circulating cooling water is in a closed type or an open type, in a closed cooling water system, the cooling water is not exposed to the air, the water loss is little, and the contents of various minerals and ions in the water are not changed generally. In the open circulating water system, the water is re-cooled by the cooling tower, so that the cooling water is contacted with air in the recycling process, part of water is evaporated and lost when passing through the cooling tower, and the content of various minerals and ions in the water is concentrated and increased.
Patent publication No. CN101412568B, entitled circulating water scale inhibitor, comprises the following components by weight: 2.5-2.8 parts of PASP (polyaspartic acid), 1-1.2 parts of ATMP (amino trimethylene phosphonic acid), 2.4-2.6 parts of HPMA (hydrolyzed polymaleic anhydride), 1.2-1.4 parts of AA/AMPS (acrylic acid and 2-acrylamide-2-methyl propanesulfonic acid copolymer), 1.1-1.3 parts of PAA (polyacrylic acid) and 0.7-1.8 parts of water.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a circulating water phosphorus-free scale inhibitor and a preparation method thereof, which solve the defects and the defects in the prior art.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a circulating water phosphorus-free scale inhibitor is prepared from the following raw materials in parts by weight:
22-28 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer,
3.5 to 4.5 parts of acrylic acid-2-methylpropanesulfonic acid copolymer,
1.25 to 1.45 parts of 2-carboxylic acid thiomorpholine,
8 to 11.5 parts of zinc salt,
23-28 parts of polymaleic anhydride,
1.75 to 2.15 parts of hydrochloric acid,
13-16.5 parts of polyaspartic acid,
2.7 to 3.2 parts of molybdate,
16-24 parts of deionized water.
Preferably, the circulating water phosphorus-free scale inhibitor is prepared from the following raw materials in parts by weight:
25 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer,
4 parts of acrylic acid-2-methylpropanesulfonic acid copolymer,
1.35 parts of 2-carboxylic acid thiomorpholine,
9.7 parts of zinc salt,
25.5 parts of polymaleic anhydride,
1.98 parts of hydrochloric acid,
14.7 parts of polyaspartic acid,
3 parts of molybdate,
And 20 parts of deionized water.
Preferably, the zinc salt is a mixture of zinc chloride and zinc nitrate.
Preferably, the mass ratio of zinc chloride to zinc nitrate in the mixture of zinc chloride and zinc nitrate is 1: 0.6 to 0.85.
Preferably, the molybdate is a mixture of sodium molybdate and potassium molybdate.
Preferably, the molybdate is a mixture of sodium molybdate and potassium molybdate, and the weight ratio of the sodium molybdate to the potassium molybdate is 1: 0.34-0.38.
The invention also provides a preparation method of the circulating water phosphorus-free scale inhibitor, which comprises the following steps:
s1, preparing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, 2-carboxylic acid thiomorpholine, zinc salt, polymaleic anhydride, hydrochloric acid, polyaspartic acid, molybdate and deionized water in parts by weight;
s2, mixing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, polymaleic anhydride and polyaspartic acid, and adding deionized water at the temperature of 44-48 ℃ to complete primary stirring;
s3, adding a mixture of 2-carboxylic acid thiomorpholine and hydrochloric acid into the materials to complete secondary stirring;
and S4, adding zinc salt and molybdate into the materials, stirring for three times, then carrying out heat preservation and standing for 15-20 min, and cooling to room temperature to obtain the circulating water phosphorus-free scale inhibitor.
Preferably, the primary stirring time is 12-15 min, the stirring speed is 600-800 r/min, the secondary stirring time is 7-10 min, the stirring speed is 400-600 r/min, the tertiary stirring time is 25-30 min, and the stirring speed is 300-400 r/min.
Preferably, the temperature of the heat preservation and standing treatment is 52-56 ℃.
(III) advantageous effects
The invention provides a circulating water non-phosphorus scale inhibitor and a preparation method thereof. The method has the following beneficial effects:
1. the circulating water non-phosphorus scale inhibitor disclosed by the invention is prepared by selecting raw materials, optimizing the content of each raw material, and selecting acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, 2-carboxylic acid thiomorpholine, zinc salt, polymaleic anhydride, hydrochloric acid, polyaspartic acid, molybdate and the like in a proper ratio, so that the advantages of the raw materials are fully exerted, the raw materials are mutually supplemented and promoted, and the quality of the product is improved; most importantly, the corrosion inhibitor has low corrosion rate, can effectively reduce the corrosion of carbon steel, copper and stainless steel, and is a high-efficiency corrosion and scale inhibitor.
2. In addition, the circulating water phosphorus-free scale inhibitor has excellent dispersion performance, and can effectively prevent the corrosion of metal equipment;
3. the coating does not contain phosphorus, is pollution-free, has partial biodegradability and is environment-friendly;
4. under high-concentration operation, the scale inhibitor has excellent scale inhibition effect on calcium scale and silicate scale (the existing scale inhibitor is generally poor in scale inhibition performance, particularly poor in scale inhibition effect on the silicate scale under high-concentration operation and cannot meet the scale inhibition requirement of long-time high-temperature operation);
5. the COD value is low, can be discharged according to the regulation, belongs to liquid commodity, and is convenient to use, operate, transport and the like.
6. The circulating water phosphorus-free scale inhibitor selects acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (mainly playing a scale inhibition role) and acrylic acid-2-methylpropanesulfonic acid copolymer (having a good synergistic effect with the acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer and being capable of greatly improving the scale inhibition effect of the circulating water phosphorus-free scale inhibitor, so that the circulating water phosphorus-free scale inhibitor can be suitable for water quality environments with high pH, high alkalinity and high hardness, and is particularly suitable for a scale inhibition dispersant running at a high concentration multiple), 2-carboxylic acid thiomorpholine (not only having an activation control function and being capable of being used as a scale inhibition dispersant with the acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, the acrylic acid-2-methylpropanesulfonic acid copolymer, a surfactant and a surfactant in a proper proportion, The polymaleic anhydride and the polyaspartic acid are matched with each other to play a good synergistic effect, so that the circulating water phosphorus-free scale inhibitor has excellent scale inhibition performance, the colloidal silica scale inhibition rate, the magnesium silicate scale inhibition rate and the calcium silicate scale inhibition rate are high, and the calcium carbonate scale inhibition rate, the calcium sulfate scale inhibition rate and the zinc stability rate are high, and the circulating water phosphorus-free scale inhibitor is suitable for inhibiting scale for a long time under a high-temperature condition; the corrosion inhibitor can form a chelate form with hydrochloric acid, greatly reduces the corrosion rate, can effectively reduce the corrosion of carbon steel, copper and stainless steel, and is a high-efficiency corrosion and scale inhibitor, zinc salt, polymaleic anhydride (mainly playing a role in scale inhibition), hydrochloric acid, polyaspartic acid (playing a role in scale inhibition and corrosion inhibition) and molybdate;
7. preferably, the zinc salt is a mixture of zinc chloride and zinc nitrate. Preferably, the mass ratio of zinc chloride to zinc nitrate in the mixture of zinc chloride and zinc nitrate is 1: 0.6 to 0.85.
The zinc chloride and the zinc nitrate are matched with each other to play a good synergistic effect and play a good role in corrosion and scale inhibition.
8. Preferably, the molybdate is a mixture of sodium molybdate and potassium molybdate. Preferably, the molybdate is a mixture of sodium molybdate and potassium molybdate, and the weight ratio of the sodium molybdate to the potassium molybdate is 1: 0.34 to 0.38.
The sodium molybdate and the potassium molybdate are matched with each other to play a good synergistic effect, so that the corrosion rate can be greatly reduced, the corrosion of carbon steel, copper and stainless steel can be effectively reduced, and the corrosion and scale inhibitor is an efficient corrosion and scale inhibitor.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
a circulating water phosphorus-free scale inhibitor is prepared from the following raw materials in parts by weight:
22-28 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer,
3.5 to 4.5 parts of acrylic acid-2-methylpropanesulfonic acid copolymer,
1.25 to 1.45 parts of 2-carboxylic acid thiomorpholine,
8 to 11.5 parts of zinc salt,
23-28 parts of polymaleic anhydride,
1.75 to 2.15 parts of hydrochloric acid,
13-16.5 parts of polyaspartic acid,
2.7 to 3.2 parts of molybdate,
16-24 parts of deionized water.
Preferably, the circulating water phosphorus-free scale inhibitor is prepared from the following raw materials in parts by weight:
25 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer,
4 parts of acrylic acid-2-methylpropanesulfonic acid copolymer,
1.35 parts of 2-carboxylic acid thiomorpholine,
9.7 parts of zinc salt,
25.5 parts of polymaleic anhydride,
1.98 parts of hydrochloric acid,
14.7 parts of polyaspartic acid,
3 parts of molybdate,
And 20 parts of deionized water.
Preferably, the zinc salt is a mixture of zinc chloride and zinc nitrate.
Preferably, the mass ratio of zinc chloride to zinc nitrate in the mixture of zinc chloride and zinc nitrate is 1: 0.6 to 0.85.
Preferably, the molybdate is a mixture of sodium molybdate and potassium molybdate.
Preferably, the molybdate is a mixture of sodium molybdate and potassium molybdate, and the weight ratio of the sodium molybdate to the potassium molybdate is 1: 0.34-0.38.
The invention also provides a preparation method of the circulating water phosphorus-free scale inhibitor, which comprises the following steps:
s1, preparing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, 2-carboxylic acid thiomorpholine, zinc salt, polymaleic anhydride, hydrochloric acid, polyaspartic acid, molybdate and deionized water in parts by weight;
s2, mixing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, polymaleic anhydride and polyaspartic acid, and adding deionized water at the temperature of 44-48 ℃ to complete primary stirring;
s3, adding a mixture of 2-carboxylic acid thiomorpholine and hydrochloric acid into the materials to complete secondary stirring;
and S4, adding zinc salt and molybdate into the materials, stirring for three times, then carrying out heat preservation and standing for 15-20 min, and cooling to room temperature to obtain the circulating water phosphorus-free scale inhibitor.
Preferably, the primary stirring time is 12-15 min, the stirring speed is 600-800 r/min, the secondary stirring time is 7-10 min, the stirring speed is 400-600 r/min, the tertiary stirring time is 25-30 min, and the stirring speed is 300-400 r/min.
Preferably, the temperature of the heat preservation and standing treatment is 52-56 ℃.
Example two:
a circulating water phosphorus-free scale inhibitor is prepared from the following raw materials in parts by weight:
22 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer,
3.5 parts of acrylic acid-2-methylpropanesulfonic acid copolymer,
1.25 parts of 2-carboxylic acid thiomorpholine,
8 portions of zinc salt,
23 parts of polymaleic anhydride,
1.75 parts of hydrochloric acid,
13 parts of polyaspartic acid,
2.7 parts of molybdate,
16 parts of deionized water.
In this example, the zinc salt is a mixture of zinc chloride and zinc nitrate.
In this embodiment, the mass ratio of zinc chloride to zinc nitrate in the mixture of zinc chloride and zinc nitrate is 1: 0.6.
in this example, the molybdate is a mixture of sodium molybdate and potassium molybdate.
In this embodiment, the molybdate is a mixture of sodium molybdate and potassium molybdate, and the mass ratio of the molybdate to the potassium molybdate is 1: 0.34.
in this embodiment, the preparation method of the phosphorus-free scale inhibitor for circulating water comprises the following steps:
s1, preparing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, 2-carboxylic acid thiomorpholine, zinc salt, polymaleic anhydride, hydrochloric acid, polyaspartic acid, molybdate and deionized water in parts by weight;
s2, mixing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, polymaleic anhydride and polyaspartic acid, and adding deionized water with the temperature of 44 ℃ to complete primary stirring;
s3, adding a mixture of 2-carboxylic acid thiomorpholine and hydrochloric acid into the materials to complete secondary stirring;
and S4, adding zinc salt and molybdate into the materials, stirring for three times, then carrying out heat preservation and standing treatment for 20min, and cooling to room temperature to obtain the circulating water phosphorus-free scale inhibitor.
In this embodiment, the primary stirring time is 12min, the stirring speed is 800r/min, the secondary stirring time is 7min, the stirring speed is 600r/min, the tertiary stirring time is 25min, and the stirring speed is 400 r/min.
In this example, the incubation and standing treatment temperature was 52 ℃.
Example three:
a circulating water phosphorus-free scale inhibitor is prepared from the following raw materials in parts by weight:
28 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer,
4.5 parts of acrylic acid-2-methylpropanesulfonic acid copolymer,
1.45 parts of 2-carboxylic acid thiomorpholine,
11.5 parts of zinc salt,
28 parts of polymaleic anhydride,
2.15 parts of hydrochloric acid,
16.5 parts of polyaspartic acid,
3.2 parts of molybdate,
And 24 parts of deionized water.
In this example, the zinc salt is a mixture of zinc chloride and zinc nitrate.
In this embodiment, the mass ratio of zinc chloride to zinc nitrate in the mixture of zinc chloride and zinc nitrate is 1: 0.85.
in this example, the molybdate is a mixture of sodium molybdate and potassium molybdate.
In this embodiment, the molybdate is a mixture of sodium molybdate and potassium molybdate, and the mass ratio of the molybdate to the potassium molybdate is 1: 0.38.
in this embodiment, the preparation method of the phosphorus-free scale inhibitor for circulating water comprises the following steps:
s1, preparing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, 2-carboxylic acid thiomorpholine, zinc salt, polymaleic anhydride, hydrochloric acid, polyaspartic acid, molybdate and deionized water in parts by weight;
s2, mixing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, polymaleic anhydride and polyaspartic acid, and adding deionized water with the temperature of 48 ℃ to complete primary stirring;
s3, adding a mixture of 2-carboxylic acid thiomorpholine and hydrochloric acid into the materials to complete secondary stirring;
and S4, adding zinc salt and molybdate into the materials, stirring for three times, then carrying out heat preservation and standing treatment for 15min, and cooling to room temperature to obtain the circulating water phosphorus-free scale inhibitor.
In this embodiment, the primary stirring time is 15min, the stirring speed is 600r/min, the secondary stirring time is 10min, the stirring speed is 400r/min, the tertiary stirring time is 30min, and the stirring speed is 300 r/min.
In this example, the incubation and standing treatment temperature was 56 ℃.
Example four:
a circulating water phosphorus-free scale inhibitor is prepared from the following raw materials in parts by weight:
25 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer,
4 parts of acrylic acid-2-methylpropanesulfonic acid copolymer,
1.35 parts of 2-carboxylic acid thiomorpholine,
9.7 parts of zinc salt,
25.5 parts of polymaleic anhydride,
1.98 parts of hydrochloric acid,
14.7 parts of polyaspartic acid,
3 parts of molybdate,
And 20 parts of deionized water.
In this example, the zinc salt is a mixture of zinc chloride and zinc nitrate.
In this embodiment, the mass ratio of zinc chloride to zinc nitrate in the mixture of zinc chloride and zinc nitrate is 1: 0.73.
in this example, the molybdate is a mixture of sodium molybdate and potassium molybdate.
In this embodiment, the molybdate is a mixture of sodium molybdate and potassium molybdate, and the mass ratio of the molybdate to the potassium molybdate is 1: 0.36.
in this embodiment, the preparation method of the phosphorus-free scale inhibitor for circulating water comprises the following steps:
s1, preparing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, 2-carboxylic acid thiomorpholine, zinc salt, polymaleic anhydride, hydrochloric acid, polyaspartic acid, molybdate and deionized water in parts by weight;
s2, mixing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, polymaleic anhydride and polyaspartic acid, and adding deionized water with the temperature of 46 ℃ to complete primary stirring;
s3, adding a mixture of 2-carboxylic acid thiomorpholine and hydrochloric acid into the materials to complete secondary stirring;
and S4, adding zinc salt and molybdate into the materials, stirring for three times, then carrying out heat preservation and standing treatment for 18min, and cooling to room temperature to obtain the circulating water phosphorus-free scale inhibitor.
In this embodiment, the primary stirring time is 14min, the stirring speed is 700r/min, the secondary stirring time is 8min, the stirring speed is 500r/min, the tertiary stirring time is 28min, and the stirring speed is 350 r/min.
In this example, the incubation and standing treatment temperature was 54 ℃.
The performance of the circulating water phosphorus-free scale inhibitor obtained in the embodiments 2 to 4 of the present invention was tested, and the test results are shown in table 1:
wherein, the colloidal silica scale inhibition rate, the magnesium silicate scale inhibition rate and the calcium silicate scale inhibition rate are as follows: the synthesis and silicon-blocking performance of AA-TBAM copolymer are tested according to the literature [ Qiu Tong, Dushujuan, Sun Yue, etc. ] chemical engineering technology, 2019, volume 27 (4):44-50 ].
Calcium carbonate scale inhibition rate, calcium sulfate scale inhibition rate and zinc stabilization rate: the tests were carried out according to the literature [ July, Chenkang, Jollili et al ] Synthesis and Properties of maleic anhydride terpolymer antisludging Agents [ J ]. Industrial Water treatment, 2015, volume 35 (3):48-51 ].
Corrosion rate: tests were performed with reference to GB13296-91 and corrosion rates were calculated.
TABLE 1
As can be seen from the above table, the circulating water phosphorus-free scale inhibitor of the present invention has excellent scale inhibition performance, high colloidal silica scale inhibition rate, high magnesium silicate scale inhibition rate, high calcium carbonate scale inhibition rate, high calcium sulfate scale inhibition rate and high zinc stability rate, and is suitable for long-time scale inhibition under high temperature conditions; most importantly, the corrosion inhibitor has low corrosion rate, can effectively reduce the corrosion of carbon steel, copper and stainless steel, and is a high-efficiency corrosion and scale inhibitor.
Comparative example 1:
the difference from example 4 is that no acrylic acid-2-methylpropanesulfonic acid copolymer is present, and the other is the same as example 4.
Tests show that the scale inhibition effect (scale inhibition rate) of the circulating water phosphorus-free scale inhibitor of the comparative example is greatly reduced compared with that of example 4, and particularly the scale inhibition rate of colloidal silica, the scale inhibition rate of magnesium silicate, the scale inhibition rate of calcium silicate and the zinc stability rate are obviously reduced.
Comparative example 2:
the difference from example 4 is that 2-carboxylic acid thiomorpholine is absent, and the other is the same as example 4.
Tests show that the scale inhibition effect (scale inhibition rate) of the circulating water phosphorus-free scale inhibitor of the comparative example is greatly reduced compared with that of example 4, particularly the scale inhibition rate of colloidal silica, the scale inhibition rate of magnesium silicate, the scale inhibition rate of calcium sulfate and the zinc stability are obviously reduced, and the corrosion rate is greatly increased.
Comparative example 3:
the difference from example 4 is that no polymaleic anhydride is present, and the other is the same as example 4.
Tests show that the scale inhibition effect (scale inhibition rate) of the circulating water phosphorus-free scale inhibitor of the comparative example is greatly reduced compared with that of example 4.
Comparative example 4:
the method is different from the method in example 4 in that the zinc salt is only zinc chloride, and the rest is the same as the method in example 4.
Tests show that the scale inhibition effect (scale inhibition rate) of the circulating water phosphorus-free scale inhibitor of the comparative example is slightly reduced compared with that of example 4, wherein the scale inhibition rate of colloidal silica, the scale inhibition rate of magnesium silicate, the scale inhibition rate of calcium silicate and the zinc stability rate are obviously reduced; and the corrosion rate is greatly increased.
Comparative example 5:
the difference from example 4 is that none of the molybdates is a mixture of sodium molybdate and potassium molybdate, and the rest is the same as example 4.
Tests show that the scale inhibition effect (scale inhibition rate) of the circulating water phosphorus-free scale inhibitor of the comparative example is not obviously changed compared with example 4, but the corrosion rate is greatly increased.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a reference structure" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A circulating water non-phosphorus scale inhibitor is characterized in that: the feed is prepared from the following raw materials in parts by weight:
22-28 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer,
3.5 to 4.5 parts of acrylic acid-2-methylpropanesulfonic acid copolymer,
1.25 to 1.45 parts of 2-carboxylic acid thiomorpholine,
8 to 11.5 parts of zinc salt,
23-28 parts of polymaleic anhydride,
1.75 to 2.15 parts of hydrochloric acid,
13-16.5 parts of polyaspartic acid,
2.7 to 3.2 parts of molybdate,
16-24 parts of deionized water.
2. The circulating water phosphorus-free scale inhibitor of claim 1, which is characterized in that: the circulating water phosphorus-free scale inhibitor is prepared from the following raw materials in parts by weight:
25 parts of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer,
4 parts of acrylic acid-2-methylpropanesulfonic acid copolymer,
1.35 parts of 2-carboxylic acid thiomorpholine,
9.7 parts of zinc salt,
25.5 parts of polymaleic anhydride,
1.98 parts of hydrochloric acid,
14.7 parts of polyaspartic acid,
3 parts of molybdate,
And 20 parts of deionized water.
3. The circulating water phosphorus-free scale inhibitor of claim 1, which is characterized in that: the zinc salt is a mixture of zinc chloride and zinc nitrate.
4. The circulating water phosphorus-free scale inhibitor of claim 3, which is characterized in that: the mass ratio of zinc chloride to zinc nitrate in the mixture of zinc chloride and zinc nitrate is 1: 0.6 to 0.85.
5. The circulating water phosphorus-free scale inhibitor of claim 1, which is characterized in that: the molybdate is a mixture of sodium molybdate and potassium molybdate.
6. The circulating water phosphorus-free scale inhibitor of claim 5, which is characterized in that: the molybdate is a mixture of sodium molybdate and potassium molybdate, wherein the weight ratio of the sodium molybdate to the potassium molybdate is 1: 0.34-0.38.
7. A preparation method of a circulating water phosphorus-free scale inhibitor is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, preparing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, 2-carboxylic acid thiomorpholine, zinc salt, polymaleic anhydride, hydrochloric acid, polyaspartic acid, molybdate and deionized water in parts by weight;
s2, mixing acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid-2-methylpropanesulfonic acid copolymer, polymaleic anhydride and polyaspartic acid, and adding deionized water at the temperature of 44-48 ℃ to complete primary stirring;
s3, adding a mixture of 2-carboxylic acid thiomorpholine and hydrochloric acid into the materials to complete secondary stirring;
and S4, adding zinc salt and molybdate into the materials, stirring for three times, then carrying out heat preservation and standing for 15-20 min, and cooling to room temperature to obtain the circulating water phosphorus-free scale inhibitor.
8. The preparation method of the circulating water phosphorus-free scale inhibitor according to claim 7, characterized in that: the primary stirring time is 12-15 min, the stirring speed is 600-800 r/min, the secondary stirring time is 7-10 min, the stirring speed is 400-600 r/min, the tertiary stirring time is 25-30 min, and the stirring speed is 300-400 r/min.
9. The preparation method of the circulating water phosphorus-free scale inhibitor according to claim 7, characterized in that: the heat preservation and standing treatment temperature is 52-56 ℃.
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| CN115028274A (en) * | 2022-08-04 | 2022-09-09 | 山东绿之能环保科技有限公司 | Oilfield reinjection water scale inhibitor with corrosion resistance function and preparation method thereof |
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