CN117164128A - Organic scale and corrosion inhibitor for high-dissolved-oxygen water quality and preparation method thereof - Google Patents
Organic scale and corrosion inhibitor for high-dissolved-oxygen water quality and preparation method thereof Download PDFInfo
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- 230000007797 corrosion Effects 0.000 title claims abstract description 91
- 238000005260 corrosion Methods 0.000 title claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003112 inhibitor Substances 0.000 title claims abstract description 56
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 36
- 239000001301 oxygen Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 19
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical class O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 claims abstract description 89
- RGZHEOWNTDJLAQ-UHFFFAOYSA-N 3,4,5-trihydroxybenzaldehyde Chemical compound OC1=CC(C=O)=CC(O)=C1O RGZHEOWNTDJLAQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 13
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- KGBNEVNDPXWACX-UHFFFAOYSA-N [O-]C(CC[S+]=C(CCC(O)=O)O)=O Chemical compound [O-]C(CC[S+]=C(CCC(O)=O)O)=O KGBNEVNDPXWACX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000005336 allyloxy group Chemical group 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 150000003384 small molecules Chemical class 0.000 claims description 10
- XUHHZNLAPUWRHH-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;methanesulfonate Chemical compound CS(O)(=O)=O.CCCCN1CN(C)C=C1 XUHHZNLAPUWRHH-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002608 ionic liquid Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000007259 addition reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 34
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 25
- 230000000694 effects Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920001661 Chitosan Polymers 0.000 description 5
- 239000000498 cooling water Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- -1 aromatic Schiff base Chemical class 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses an organic scale and corrosion inhibitor for high-dissolved-oxygen water quality and a preparation method thereof, and relates to the technical field of water treatment. The organic scale and corrosion inhibitor for high-dissolved oxygen water quality comprises the following raw materials in parts by weight: 30-45 parts of modified chitosan oligosaccharide, 15-20 parts of S-carboxyethyl thiosuccinic acid, 10-15 parts of allyloxy polyether carboxylate copolymer, 10-15 parts of polyepoxysuccinic acid and 10-25 parts of deionized water. The invention firstly prepares carboxylated chitosan oligosaccharide through the reaction of chitosan oligosaccharide and itaconic acid, then prepares a novel modified chitosan oligosaccharide through the condensation reaction of carboxylated chitosan oligosaccharide and 3,4, 5-trihydroxybenzaldehyde, and provides a specific preparation method; the compound organic scale and corrosion inhibitor containing the modified chitosan oligosaccharide provided by the invention has excellent scale inhibition and corrosion inhibition performances in a high-dissolved-oxygen water quality system.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to an organic scale and corrosion inhibitor for high-dissolved-oxygen water quality and a preparation method thereof.
Background
The industrial circulating cooling water increases along with the increase of the repeated use times, the concentration of metal ions in the water increases along with the increase, insoluble salt is easy to form to deposit and scale on the surface of the heat exchanger, the corrosion of metal equipment is caused, the service life of the equipment is shortened, and the addition of the scale and corrosion inhibitor into the circulating cooling water system is an effective method for slowing down the scale and corrosion.
With the continuous improvement of environmental protection requirements, water treatment chemicals gradually develop to green, efficient and proprietary. The scale and corrosion inhibitor which is usually adopted in the current market and has no phosphorus or low phosphorus has expected effect, and the dosage of the medicament is relatively large. In a circulating water system with high dissolved oxygen water quality, a large amount of inorganic corrosion inhibitors are also required to be compounded for use, the use of the inorganic corrosion inhibitors can cause secondary pollution to the environment, and the stability in the circulating water is poor, so that medicament deposition or precipitation is caused.
The Chinese patent application with publication number of CN116768379A discloses a high-temperature-resistant corrosion-resistant scale inhibitor, a preparation method and application thereof, and provides a novel graft modified hybrid polymer for scale and corrosion inhibition, wherein the high-temperature-resistant corrosion-resistant scale inhibitor containing the graft modified hybrid polymer has a corrosion inhibition rate of 92.17% in the optimal embodiment disclosed in the patent, but has relatively poor corrosion inhibition rate in high-dissolved oxygen water quality.
The Chinese patent application with publication number of CN114772754A discloses a circulating cooling water scale and corrosion inhibitor and a preparation method thereof, and the compound circulating cooling water scale and corrosion inhibitor containing the adsorption polymer corrosion inhibitor provided by the patent application has excellent scale and corrosion inhibition performance and wide practicability, and has better protectiveness on carbon steel, stainless steel, copper and other material equipment. However, in the practical application of the water with high dissolved oxygen, the corrosion inhibition rate is lower than 85 percent, and the corrosion inhibition effect cannot be expected.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an organic scale and corrosion inhibitor for water quality with high dissolved oxygen and a preparation method thereof.
In order to achieve the above object, the present invention is realized by the following technical scheme:
an organic scale and corrosion inhibitor for high-dissolved oxygen water quality comprises the following raw materials in parts by weight:
30-45 parts of modified chitosan oligosaccharide, 15-20 parts of S-carboxyethyl thiosuccinic acid, 10-15 parts of allyloxy polyether carboxylate copolymer, 10-15 parts of polyepoxysuccinic acid and 10-25 parts of deionized water;
the modified chitosan oligosaccharide has a structural formula shown in a formula (I):
（I）。
the modified chitosan oligosaccharide is prepared by preparing carboxylated chitosan oligosaccharide from chitosan oligosaccharide and itaconic acid through an addition reaction, and then carrying out a condensation reaction on the carboxylated chitosan oligosaccharide and 3,4, 5-trihydroxybenzaldehyde, wherein the number average molecular weight of the modified chitosan oligosaccharide is 3500-5000, and the reaction equation is as follows:
。
where n=o+p, q+s=o, r+t=p, n, o, p, q, r, s, t are natural numbers greater than 0.
Further, the modified chitosan oligosaccharide is prepared by the following method:
s1: sequentially adding 1000 parts by weight of DMF solvent, 330-380 parts by weight of chitosan oligosaccharide and 1-2 parts by weight of 1-butyl-3-methylimidazole methane sulfonate ionic liquid into a reaction kettle, stirring and uniformly mixing, and heating to 95 ℃;
s2: dropwise adding 550 parts by weight of DMF solution containing 230-260 parts by weight of itaconic acid into a reaction kettle, slowly dropwise adding for 2-3h, controlling the temperature to be 92-98 ℃, and heating to 105-110 ℃ after the dropwise adding is finished, and continuing to react for 3-4h;
s3: starting a vacuum pump, and removing small molecules and solvent under vacuum of 0.06MPa to obtain carboxylated chitosan oligosaccharide;
s4: cooling to 60-70 ℃, slowly adding 800-1000 parts by weight of absolute ethyl alcohol, stirring and dissolving uniformly, and then adding 2-3 parts by weight of acetic acid;
s5: adding 280-320 parts by weight of 3,4, 5-trihydroxybenzaldehyde into a reaction kettle, stirring and uniformly mixing, heating to 90-100 ℃, and reacting for 8-9h;
s6: starting a vacuum pump, and removing small molecules and solvent under vacuum of 0.06MPa to obtain reddish brown viscous liquid;
s7: cooling to 25-45 ℃, slowly adding 400-600 parts by weight of deionized water, uniformly stirring, and filtering to obtain the modified chitosan oligosaccharide with the solid content of 40-45 wt%.
The number average molecular weight of the chitosan oligosaccharide is 1100-2200.
The modified chitosan oligosaccharide belongs to a macromolecular environment-friendly green corrosion inhibitor, contains a large amount of hydroxyl and amino, and is used for preparing aromatic Schiff base by 3,4, 5-trihydroxybenzaldehyde, N atoms form stable coordination bonds with d orbitals on the surface of iron by virtue of lone pair electrons, so that the oxygen electrode activation energy is improved, the corrosion rate is effectively reduced, and the C=N double bonds contained in the modified chitosan oligosaccharide are extremely easy to form stable complexes with metal to further prevent metal corrosion; on the other hand, the self-assembly film forming speed of the aromatic Schiff base is high, and a protective film can be formed rapidly to block O 2 And/metal electron transfer, which effectively controls the metal corrosion of the high-dissolved oxygen water quality system. The solubility of chitosan oligosaccharide is effectively solved through carboxylation, the scale inhibition capability is endowed, a large number of scale inhibition groups are uniformly distributed on the surface of the protective film, and the formation of scale layers or the adsorption of sediments on the surface of metal is effectively prevented.
The preparation method of the organic scale and corrosion inhibitor for high-dissolved oxygen water quality comprises the following steps:
s1: weighing raw materials according to the composition of the raw materials;
s2: sequentially adding the metered modified chitosan oligosaccharide, the allyloxy polyether carboxylate copolymer, the polyepoxysuccinic acid and the deionized water into a reaction kettle, and stirring at room temperature for 20-30min;
s3: slowly adding the metered S-carboxyethyl thiosuccinic acid into a reaction kettle, and uniformly stirring for 20-50min at room temperature to obtain the organic scale and corrosion inhibitor for water quality with high dissolved oxygen.
By adopting the technical scheme, the beneficial effects of the invention include:
(1) The invention firstly prepares carboxylated chitosan oligosaccharide through the reaction of chitosan oligosaccharide and itaconic acid, then prepares novel modified chitosan oligosaccharide through the condensation reaction of carboxylated chitosan oligosaccharide and 3,4, 5-trihydroxybenzaldehyde, and provides a specific preparation method.
(2) The compound organic scale and corrosion inhibitor containing the modified chitosan oligosaccharide provided by the invention has excellent scale inhibition and corrosion inhibition performances in a high-dissolved-oxygen water quality system.
Detailed Description
The present invention is further described below with reference to examples, but the present invention is not limited to these examples.
Example 1
Preparation of modified chitosan oligosaccharide:
s1: sequentially adding 100kg of DMF solvent, 36kg of chitosan oligosaccharide (with the number average molecular weight of 1850) and 0.12kg of 1-butyl-3-methylimidazole methane sulfonate ionic liquid into a reaction kettle, stirring and mixing uniformly, and heating to 95 ℃;
s2: dropwise adding 55kg of DMF solution containing 24.5kg of itaconic acid into the reaction kettle, slowly dropwise adding 2.5h, controlling the temperature to be 92-98 ℃, and heating to 105-110 ℃ after the dropwise adding is finished to continue to react for 3.5h;
s3: starting a vacuum pump, and removing small molecules and solvent under vacuum of 0.06MPa to obtain carboxylated chitosan oligosaccharide;
s4: cooling to 65 ℃, slowly adding 90kg of absolute ethyl alcohol, stirring and dissolving uniformly, and then adding 0.23kg of acetic acid;
s5: adding 30kg of 3,4, 5-trihydroxybenzaldehyde into a reaction kettle, stirring and mixing uniformly, heating to 95 ℃ and reacting for 8.5h;
s6: starting a vacuum pump, and removing small molecules and solvent under vacuum of 0.06MPa to obtain reddish brown viscous liquid;
s7: cooling to 40 ℃, slowly adding 50kg of deionized water, stirring uniformly, and filtering to obtain the modified chitosan oligosaccharide with the solid content of 43.4wt% and the number average molecular weight of 4475.
Example 2
Preparation of modified chitosan oligosaccharide:
s1: sequentially adding 100kg of DMF solvent, 33kg of chitosan oligosaccharide (with the number average molecular weight of 1187) and 0.1kg of 1-butyl-3-methylimidazole methane sulfonate ionic liquid into a reaction kettle, stirring and mixing uniformly, and heating to 95 ℃;
s2: dropwise adding 55kg of DMF solution containing 23kg of itaconic acid into the reaction kettle, slowly dropwise adding for 2 hours, controlling the temperature to be 92-98 ℃, and heating to 105-110 ℃ after the dropwise adding is finished, and continuing to react for 3 hours;
s3: starting a vacuum pump, and removing small molecules and solvent under vacuum of 0.06MPa to obtain carboxylated chitosan oligosaccharide;
s4: cooling to 60 ℃, slowly adding 80kg of absolute ethyl alcohol, stirring and dissolving uniformly, and then adding 0.2kg of acetic acid;
s5: adding 28kg of 3,4, 5-trihydroxybenzaldehyde into a reaction kettle, stirring and mixing uniformly, heating to 90 ℃, and reacting for 8 hours;
s6: starting a vacuum pump, and removing small molecules and solvent under vacuum of 0.06MPa to obtain reddish brown viscous liquid;
s7: cooling to 25 ℃, slowly adding 40kg of deionized water, stirring uniformly, and filtering to obtain the modified chitosan oligosaccharide with the solid content of 40.8wt% and the number average molecular weight of 3594.
Example 3
Preparation of modified chitosan oligosaccharide:
s1: sequentially adding 100kg of DMF solvent, 38kg of chitosan oligosaccharide (with the number average molecular weight of 2135) and 0.2kg of 1-butyl-3-methylimidazole methane sulfonate ionic liquid into a reaction kettle, stirring and mixing uniformly, and heating to 95 ℃;
s2: dropwise adding 55kg of DMF solution containing 26kg of itaconic acid into the reaction kettle, slowly dropwise adding for 3 hours, controlling the temperature to be 92-98 ℃, and heating to 105-110 ℃ after the dropwise adding is finished for continuous reaction for 4 hours;
s3: starting a vacuum pump, and removing small molecules and solvent under vacuum of 0.06MPa to obtain carboxylated chitosan oligosaccharide;
s4: cooling to 70 ℃, slowly adding 100kg of absolute ethyl alcohol, stirring and dissolving uniformly, and then adding 0.3kg of acetic acid;
s5: adding 32kg of 3,4, 5-trihydroxybenzaldehyde into a reaction kettle, stirring and mixing uniformly, heating to 100 ℃, and reacting for 9 hours;
s6: starting a vacuum pump, and removing small molecules and solvent under vacuum of 0.06MPa to obtain reddish brown viscous liquid;
s7: cooling to 45 ℃, slowly adding 60kg of deionized water, stirring uniformly, and filtering to obtain the modified chitosan oligosaccharide with the solid content of 44.3wt% and the number average molecular weight of 4976.
Example 4
Preparation of organic scale and corrosion inhibitor for high-dissolved oxygen water quality:
s1: 40kg of modified chitosan oligosaccharide (prepared in example 1), 18kg of S-carboxyethyl thiosuccinic acid, 12kg of allyloxy polyether carboxylate copolymer (number average molecular weight: 4215), 12kg of polyepoxysuccinic acid and 20kg of deionized water are weighed;
s2: sequentially adding the weighed modified chitosan oligosaccharide, allyloxy polyether carboxylate copolymer, polyepoxysuccinic acid and deionized water into a reaction kettle, and stirring at room temperature for 25min;
s3: slowly adding the weighed S-carboxyethyl thiosuccinic acid into a reaction kettle, and uniformly stirring for 35min at room temperature to obtain the organic scale and corrosion inhibitor for high-dissolved-oxygen water quality.
Example 5
Preparation of organic scale and corrosion inhibitor for high-dissolved oxygen water quality:
s1: 30kg of modified chitosan oligosaccharide (prepared in example 2), 15kg of S-carboxyethyl thiosuccinic acid, 10kg of allyloxy polyether carboxylate copolymer (number average molecular weight: 4215), 10kg of polyepoxysuccinic acid and 10kg of deionized water are weighed;
s2: sequentially adding the weighed modified chitosan oligosaccharide, allyloxy polyether carboxylate copolymer, polyepoxysuccinic acid and deionized water into a reaction kettle, and stirring at room temperature for 20min;
s3: slowly adding the weighed S-carboxyethyl thiosuccinic acid into a reaction kettle, and uniformly stirring for 20min at room temperature to obtain the organic scale and corrosion inhibitor for high-dissolved-oxygen water quality.
Example 6
Preparation of organic scale and corrosion inhibitor for high-dissolved oxygen water quality:
s1: 45kg of modified chitosan oligosaccharide (prepared in example 3), 20kg of S-carboxyethyl thiosuccinic acid, 15kg of allyloxy polyether carboxylate copolymer (number average molecular weight: 4215), 15kg of polyepoxysuccinic acid and 25kg of deionized water are weighed;
s2: sequentially adding the weighed modified chitosan oligosaccharide, allyloxy polyether carboxylate copolymer, polyepoxysuccinic acid and deionized water into a reaction kettle, and stirring at room temperature for 30min;
s3: and slowly adding the weighed S-carboxyethyl thiosuccinic acid into a reaction kettle, and uniformly stirring for 50min at room temperature to obtain the organic scale and corrosion inhibitor for high-dissolved-oxygen water quality.
Comparative example 1
The scale and corrosion inhibitor was prepared in substantially the same manner as in example 4, except that the modified chitosan oligosaccharide used in step S1 had a number average molecular weight of 3249.
The modified chitosan oligosaccharide with the number average molecular weight of 3249 is prepared by the following method:
the preparation method of the modified chitosan oligosaccharide was substantially the same as in example 2, except that 28kg of 3,4, 5-trihydroxybenzaldehyde was replaced with 23kg of 3,4, 5-trihydroxybenzaldehyde in step S5.
Comparative example 2
The scale and corrosion inhibitor was prepared in substantially the same manner as in example 4, except that the modified chitosan oligosaccharide used in step S1 had a number average molecular weight of 5482.
The modified chitosan oligosaccharide with the number average molecular weight of 5482 was prepared by the following method:
the preparation method of the modified chitosan oligosaccharide was basically the same as that of example 3, except that in step S2, 55kg of DMF solution containing 26kg of itaconic acid was replaced with 55kg of DMF solution containing 30kg of itaconic acid; in step S5, 32kg of 3,4, 5-trihydroxybenzaldehyde was replaced with 34kg of 3,4, 5-trihydroxybenzaldehyde.
Comparative example 3
The scale and corrosion inhibitor was prepared in the same manner as in example 4 except that no modified chitosan oligosaccharide was added in step S2.
Comparative example 4
The scale and corrosion inhibitor was prepared in substantially the same manner as in example 4 except that the weight of the modified chitosan oligosaccharide in step S1 was 20kg.
Comparative example 5
The scale and corrosion inhibitor was prepared in substantially the same manner as in example 4, except that in step S1, the modified chitosan oligosaccharide was replaced with an equivalent weight of the carboxylated chitosan oligosaccharide prepared in step S3 of example 1.
Comparative example 6
The scale and corrosion inhibitor was prepared in substantially the same manner as in example 4, except that in step S1, the modified chitosan oligosaccharide was replaced with an equivalent weight of chitosan oligosaccharide (number average molecular weight 1850).
Comparative example 7
The scale and corrosion inhibitor was prepared in substantially the same manner as in example 4 except that in step S1, the modified chitosan oligosaccharide was replaced with 16kg of chitosan oligosaccharide (number average molecular weight 1850), 10.8kg of itaconic acid and 13.3kg of 3,4, 5-trihydroxybenzaldehyde.
Comparative example 8
The preparation method of the scale and corrosion inhibitor is basically the same as that of the example 4, and the difference is that in the step S1, the modified chitosan oligosaccharide is replaced by the modified chitosan; the modified chitosan was prepared in substantially the same manner as in example 1 except that 36kg of chitosan oligosaccharide (number average molecular weight 1850) was replaced with chitosan of equal weight (number average molecular weight 21564) in step S1.
Comparative example 9
The scale and corrosion inhibitor was prepared in substantially the same manner as in example 4, except that in step S1, the modified chitosan oligosaccharide was replaced with an equivalent weight of a graft modified hetero-chain polymer (prepared by the method of example 1 of the invention of publication No. CN116768379 a).
Comparative example 10
The scale and corrosion inhibitor was prepared in substantially the same manner as in example 4, except that in step S1, the modified chitosan oligosaccharide was replaced with an adsorptive polymer corrosion inhibitor of equal weight (prepared by the method of example 1 of the invention of publication No. CN114772754 a).
Comparative example 11
And (3) preparing a circulating cooling water scale and corrosion inhibitor:
prepared by a method of an invention patent of publication No. CN114772754A, example 3.
The organic scale and corrosion inhibitor for high-dissolved-oxygen water quality prepared by the embodiment of the invention and the scale and corrosion inhibitor prepared by the comparative example are subjected to scale and corrosion inhibition performance test under the condition of high-dissolved-oxygen water quality, test water is taken in situ by using a high-dissolved-oxygen water quality system, and the water quality index at 25 ℃ is as follows:
dissolved oxygen: 13.6mg/L, pH:7.82, conductivity: 1752 μs/cm, calcium hardness: 162mg/L, basicity: 117mg/L, chloride: 139mg/L.
Drug concentration at test: 20mg/L, a test magnification of 4.0, standard corrosion hanging piece material of 20# carbon steel, test procedures are carried out according to GB/T18832-2008 and GB/T18175-2014, and test results are shown in table 1.
TABLE 1
As can be seen from examples 4,5 and 6 in Table 1, the organic scale and corrosion inhibitor prepared by the method has a corrosion inhibition rate of 90% in high-dissolved-oxygen water quality, a scale inhibition rate of more than 97%, and excellent scale inhibition and corrosion inhibition performances in a high-dissolved-oxygen water quality system.
Comparative examples 1 and 2 are comparative examples different from example 4 in that the modified chitosan oligosaccharide used was different in number average molecular weight, and as can be seen from the data of table 1, the corrosion inhibition rate was less than 87% when the number average molecular weight of the modified chitosan oligosaccharide was less than 3500 and more than 5000.
Comparative examples 3 and 4 are comparative examples without adding modified chitosan oligosaccharide and with the addition amount of the modified chitosan oligosaccharide of 20kg, and test data in table 1 show that the scale and corrosion inhibition effect of the scale and corrosion inhibitor compounded by reducing or without adding the modified chitosan oligosaccharide is obviously reduced, the scale inhibition rate is lower than 96%, and the corrosion inhibition rate is lower than 86%.
Comparative example 5 is a scale and corrosion inhibitor prepared by replacing modified chitosan oligosaccharide with carboxylated chitosan oligosaccharide with equal weight, and as can be seen from the data in table 1, the scale and corrosion inhibitor prepared by using carboxylated chitosan oligosaccharide has a corrosion inhibition rate of only 83.72%, and the corrosion inhibition effect cannot be expected.
Comparative example 6 is a comparative example of a scale and corrosion inhibitor prepared directly with chitosan oligosaccharide without modification of chitosan oligosaccharide, and it can be seen from the data of table 1 that the scale and corrosion inhibitor prepared with chitosan oligosaccharide has a corrosion inhibition rate of only 81.54% and a corrosion inhibition effect which cannot be expected.
Comparative example 7 is a scale and corrosion inhibitor prepared directly from chitosan oligosaccharide (number average molecular weight 1850), itaconic acid and 3,4, 5-trihydroxybenzaldehyde without modification of chitosan oligosaccharide, and the data in table 1 shows that the corrosion inhibition rate is lower than 80%, and the corrosion inhibition effect cannot be expected.
Comparative example 8 is a comparative example prepared by using modified chitosan, and the corrosion inhibition effect is only 73.69% because of the problem of chitosan solubility, and the corrosion inhibition effect cannot be expected.
Comparative example 9 is a comparative example of a scale and corrosion inhibitor prepared by adopting a graft modified hybrid chain polymer, and the data show that the scale and corrosion inhibitor has excellent scale and corrosion inhibition effect, but the corrosion inhibition rate is lower than 85% in a high-dissolved-oxygen water quality system, and the corrosion inhibition effect cannot be expected.
The comparative examples 10 and 11 show that the scale and corrosion inhibitor prepared by the adsorptive polymer corrosion inhibitor in the patent CN114772754A has a corrosion inhibition rate lower than 85% in a high-dissolved-oxygen water quality system, and the corrosion inhibition effect cannot be expected.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention; however, those skilled in the art can make various changes, modifications and variations equivalent to the above-described embodiments without departing from the scope of the technical solution of the present invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the present invention.
Claims (5)
1. The organic scale and corrosion inhibitor for the high-dissolved-oxygen water quality is characterized by comprising the following raw materials in parts by weight:
30-45 parts of modified chitosan oligosaccharide, 15-20 parts of S-carboxyethyl thiosuccinic acid, 10-15 parts of allyloxy polyether carboxylate copolymer, 10-15 parts of polyepoxysuccinic acid and 10-25 parts of deionized water;
the modified chitosan oligosaccharide has a structural formula shown in a formula (I):
（I）。
2. the organic scale and corrosion inhibitor for high-dissolved-oxygen water quality, which is characterized in that the modified chitosan oligosaccharide is prepared by firstly preparing carboxylated chitosan oligosaccharide from chitosan oligosaccharide and itaconic acid through an addition reaction, and then carrying out a condensation reaction on the carboxylated chitosan oligosaccharide and 3,4, 5-trihydroxybenzaldehyde; the number average molecular weight of the modified chitosan oligosaccharide is 3500-5000.
3. The organic scale and corrosion inhibitor for water quality with high dissolved oxygen as claimed in claim 2, wherein the number average molecular weight of the chitosan oligosaccharide is 1100-2200.
4. The organic scale and corrosion inhibitor for high-dissolved-oxygen water quality according to claim 1, wherein the modified chitosan oligosaccharide is prepared by the following method:
s1: sequentially adding 1000 parts by weight of DMF solvent, 330-380 parts by weight of chitosan oligosaccharide and 1-2 parts by weight of 1-butyl-3-methylimidazole methane sulfonate ionic liquid into a reaction kettle, stirring and uniformly mixing, and heating to 95 ℃;
s2: dropwise adding 550 parts by weight of DMF solution containing 230-260 parts by weight of itaconic acid into a reaction kettle, slowly dropwise adding for 2-3h, controlling the temperature to be 92-98 ℃, and heating to 105-110 ℃ after the dropwise adding is finished, and continuing to react for 3-4h;
s3: starting a vacuum pump, and removing small molecules and solvent under vacuum of 0.06MPa to obtain carboxylated chitosan oligosaccharide;
s4: cooling to 60-70 ℃, slowly adding 800-1000 parts by weight of absolute ethyl alcohol, stirring and dissolving uniformly, and then adding 2-3 parts by weight of acetic acid;
s5: adding 280-320 parts by weight of 3,4, 5-trihydroxybenzaldehyde into a reaction kettle, stirring and uniformly mixing, heating to 90-100 ℃, and reacting for 8-9h;
s6: starting a vacuum pump, and removing small molecules and solvent under vacuum of 0.06MPa to obtain reddish brown viscous liquid;
s7: cooling to 25-45 ℃, slowly adding 400-600 parts by weight of deionized water, uniformly stirring, and filtering to obtain the modified chitosan oligosaccharide with the solid content of 40-45 wt%.
5. A method for preparing the organic scale and corrosion inhibitor for water quality with high dissolved oxygen as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
s1: weighing raw materials according to the composition of the raw materials;
s2: sequentially adding the metered modified chitosan oligosaccharide, the allyloxy polyether carboxylate copolymer, the polyepoxysuccinic acid and the deionized water into a reaction kettle, and stirring at room temperature for 20-30min;
s3: slowly adding the metered S-carboxyethyl thiosuccinic acid into a reaction kettle, and uniformly stirring for 20-50min at room temperature to obtain the organic scale and corrosion inhibitor for water quality with high dissolved oxygen.
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| EP0828771A1 (en) * | 1995-05-24 | 1998-03-18 | Degussa Aktiengesellschaft | Graft copolymers based on mono-, oligo- and polysaccharides, process for preparing the same and their use |
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| US20140256880A1 (en) * | 2011-11-04 | 2014-09-11 | Akzo Nobel Chemicals International B.V. | Hybrid dendrite copolymers, compositions thereof and methods for producing the same |
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