CN114853188A - Phosphorus-free scale and corrosion inhibitor for heat supply network and preparation method and application thereof - Google Patents
Phosphorus-free scale and corrosion inhibitor for heat supply network and preparation method and application thereof Download PDFInfo
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- CN114853188A CN114853188A CN202210429331.1A CN202210429331A CN114853188A CN 114853188 A CN114853188 A CN 114853188A CN 202210429331 A CN202210429331 A CN 202210429331A CN 114853188 A CN114853188 A CN 114853188A
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- heat supply
- supply network
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- corrosion inhibitor
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- 230000007797 corrosion Effects 0.000 title claims abstract description 92
- 238000005260 corrosion Methods 0.000 title claims abstract description 92
- 239000003112 inhibitor Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 38
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 229920005610 lignin Polymers 0.000 claims abstract description 15
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 33
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 10
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- -1 methyl tertiary amine Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000005639 Lauric acid Substances 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 4
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- 229920005550 ammonium lignosulfonate Polymers 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- XPXMKIXDFWLRAA-UHFFFAOYSA-N hydrazinide Chemical compound [NH-]N XPXMKIXDFWLRAA-UHFFFAOYSA-N 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 229910000019 calcium carbonate Inorganic materials 0.000 description 10
- 239000003814 drug Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002455 scale inhibitor Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LIPIURJJRUOGSS-UHFFFAOYSA-N dodecyl hydrogen carbonate Chemical compound CCCCCCCCCCCCOC(O)=O LIPIURJJRUOGSS-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
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 discloses a phosphorus-free scale and corrosion inhibitor for a heat supply network and a preparation method and application thereof, belonging to the technical field of water treatment agents for water systems of heat supply network water systems, wherein the phosphorus-free scale and corrosion inhibitor comprises the following components in percentage by mass: a mixture of mono-or poly-organic carboxylic acids containing 2 to 14 carbon atoms, 5.0 to 30.0% lignin derivatives; 5.0-10.0% of hydrolyzed polymaleic anhydride; 2.0-10.0% of an organic amine mixture; 1.0-5.0% of a surfactant; 0.5-2.0% of molybdate; the balance of deionized water; the proportion of each component is 100 percent; the invention mainly solves the problems of high phosphorus content and low scale and corrosion inhibition performance of the existing heat supply network agent of the heat supply network system, is green and environment-friendly, can effectively prevent scaling and corrosion phenomena in the heat supply network system, has good corrosion inhibition effect, and ensures high-efficiency and safe operation of the heat supply network system.
Description
Technical Field
The invention belongs to the technical field of water treatment agents for water systems of heat supply pipe networks, and particularly relates to a phosphorus-free scale and corrosion inhibitor for a heat supply pipe network, and a preparation method and application thereof.
Background
At present, the problems of corrosion and scaling of a heat exchanger of a heat supply and heat supply network system and corrosion of the heat supply network are increasingly prominent, and even the civil heating and the quality of steam and water of a unit are influenced. The leakage of a plurality of heaters of a heat supply network system is caused due to the problems of process and control, the safe and economic operation of a unit is seriously influenced, and particularly, the heaters are quitted from operation due to the leakage and the scaling of the heaters, the urban heating in winter is influenced, and other unsafe factors are caused. The existing scale and corrosion inhibitor for the heat supply network has high phosphorus content, is easy to decompose at high temperature to generate phosphoric acid scale, and is easy to cause secondary pollution to water.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a phosphorus-free scale and corrosion inhibitor for a heat supply network, and a preparation method and application thereof, which are used for solving the technical problems that the existing scale and corrosion inhibitor for the heat supply network is high in phosphorus content, easy to decompose at high temperature, easy to generate phosphate scale and easy to cause secondary pollution to water.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a phosphorus-free scale and corrosion inhibitor for a heat supply network, which comprises the following components in percentage by mass: 5.0-20.0% of organic carboxylic acid mixture, 5.0-30.0% of lignin derivative, 5.0-10.0% of hydrolyzed polymaleic anhydride, 2.0-10.0% of organic amine mixture, 1.0-5.0% of surfactant, 0.5-2.0% of molybdate and the balance of deionized water.
Further, the organic carboxylic acid mixture is one or more of citric acid, gluconic acid, lauric acid polymer, dialkyl fatty carboxylic acid, capric acid, epoxy succinic acid and epoxy succinic acid; the organic carboxylic acid mixture is a mono-or poly-organic carboxylic acid mixture with 2-14 carbon atoms.
Further, the lignin derivative is one or more of sodium lignosulfonate, potassium lignosulfonate, ammonium lignosulfonate, sodium lignin humate and potassium lignin humate; the molecular weight of the lignin derivative is 200-5000.
Further, the molecular weight of the hydrolyzed polymaleic anhydride is 200-800.
Further, the organic amine mixture is one or more of triethanolamine, methyl tertiary amine, methoxypropylamine, aminoamide, ethylene tetramine and dodecylamine.
Further, the surfactant is one or more of polyoxyethylene ether, lauryl fatty alcohol polyoxyethylene ether and nonylphenol polyoxyethylene ether.
Further, the molybdate is one or more of ammonium molybdate, potassium molybdate, sodium molybdate and zinc molybdate.
The invention also discloses a preparation method of the phosphorus-free scale and corrosion inhibitor for the heat supply network, which comprises the following steps:
step 1: mixing an organic carboxylic acid mixture, a lignin derivative and hydrolyzed polymaleic anhydride, heating, uniformly stirring, and standing to obtain a mixed solution;
step 2: and adding an organic amine mixture and a surfactant into the mixed solution, stirring, adding molybdate and deionized water, and stirring and cooling to obtain the phosphorus-free scale and corrosion inhibitor for the heat supply network.
Further, in the step 1, heating to 40-65 ℃, stirring at a rotating speed of 80-160r/min for 15-20 min, and standing for 10-20 min; in the step 2, adding an organic amine mixture and a surfactant into the mixed solution, and stirring for 10-30 min; adding molybdate and deionized water, and stirring for 0.5-l.0h; stirring and cooling to room temperature.
The invention also discloses application of the heat supply network phosphorus-free scale and corrosion inhibitor in removing corrosion dirt of a heat supply network system.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a phosphorus-free scale and corrosion inhibitor for a heat supply network, which comprises the following components in percentage by mass: 5.0-20.0% of organic carboxylic acid mixture, 5.0-30.0% of lignin derivative, 5.0-10.0% of hydrolyzed polymaleic anhydride, 2.0-10.0% of organic amine mixture, 1.0-5.0% of surfactant, 0.5-2.0% of molybdate and the balance of deionized water. The mixture of the C2-14 mono-or poly-organic carboxylic acids has a large number of polar groups, is very hydrophilic and water-soluble, can perform a complex reaction with various ions, and particularly can change lattice scaling of calcium salt and disperse calcium carbonate crystals so that the calcium carbonate crystals cannot be attached; meanwhile, the synergistic effect of various functional groups can effectively improve the solubility of the scale forming compound, so that the scale inhibition performance of the scale forming compound is greatly improved; the lignin derivative is a natural reproducible high molecular polymer, has strong dispersing capacity, can disperse solids in an aqueous medium, can be adsorbed on the surfaces of various solid particles, has an exchange effect with metal ions, and has stable chemical stability and biodegradability; the hydrolyzed polymaleic anhydride is a low molecular weight polyelectrolyte with the molecular weight of 200-; the organic amine can exist in a water body in a highly dispersed state, and is enriched after contacting with the metal surface, so that the scale and corrosion inhibitor can locally reach a high concentration on a contact surface, the metal corrosion is effectively inhibited, and the adhesion of dirt on the metal surface is inhibited by the synergy of the scale and corrosion inhibitor and other effective components; the molybdate is effective in inhibiting the corrosion process and when ions contact the metal substrate, a protective passivating oxide layer is formed on the metal to prevent corrosion. The phosphorus-free scale and corrosion inhibitor for the heat supply network disclosed by the invention has good scale and corrosion inhibition performance, avoids the problems of decomposition of the phosphorus-containing scale and corrosion inhibitor to form phosphoric acid scale and high phosphorus content in water, and can be used in a wide pH range and a high temperature suitable for heat supply network water.
The invention also discloses a preparation method of the phosphorus-free scale and corrosion inhibitor for the heat supply network, the method has simple steps, is green and environment-friendly, does not discharge three wastes, mainly comprises renewable resources and biodegradable environment-friendly medicaments as main components, accords with the development direction of environment-friendly requirements and water treatment medicaments, and can be produced in large scale.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Unless otherwise specified herein, "comprising," including, "" containing, "" having, "or the like, means" consisting of … … "and" consisting essentially of … …, "e.g.," a comprises a "means" a comprises a and the other, "and" a comprises a only.
In the present context, for the sake of brevity, all possible combinations of various features in various embodiments or examples are not described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
A preparation method of a phosphorus-free scale and corrosion inhibitor for a heat supply network comprises the following steps:
step 1: mixing 15% of gluconic acid, a mixture of epoxy succinic acid and citric acid, 20% of sodium lignosulfonate and 6% of hydrolyzed polymaleic anhydride with the molecular weight of 500 in percentage by mass, heating to 60 ℃, stirring at the rotating speed of 80r/min for 15min, and standing for 10min to obtain a mixed solution.
Step 2: and adding a mixture of 5% of triethanolamine and methyl tertiary amine and 2.0% of surfactant polyoxyethylene ether into the mixed solution, stirring for 10min, adding 1.0% of potassium molybdate and 51% of deionized water, stirring for 0.5h, and cooling to room temperature to obtain the heat supply network phosphorus-free scale and corrosion inhibitor.
Example 2
A preparation method of a phosphorus-free scale and corrosion inhibitor for a heat supply network comprises the following steps:
step 1: mixing 10% of lauric acid polymer, a mixture of epoxy succinic acid and citric acid, 25% of ammonium lignosulfonate and 8% of hydrolyzed polymaleic anhydride with the molecular weight of 400 in percentage by mass, heating to 40 ℃, stirring at the rotating speed of 100r/min for 20min, and standing for 15min to obtain a mixed solution.
Step 2: adding 8% of a mixture of triethanolamine and methoxypropylamine and 3.0% of surfactant lauryl carbonate polyoxyethylene ether into the mixed solution, stirring for 10min, adding 2.0% of potassium molybdate and 44% of deionized water, stirring for 0.5h, and cooling to room temperature to obtain the heat supply network phosphorus-free scale and corrosion inhibitor.
Example 3
A preparation method of a phosphorus-free scale and corrosion inhibitor for a heat supply network comprises the following steps:
step 1: mixing 5% of dialkyl fatty acid carboxylic acid, a mixture of capric acid and epoxy succinic acid, 30% of sodium lignosulfonate and 10% of hydrolytic polymaleic anhydride with the molecular weight of 300 in percentage by mass, heating to 65 ℃, stirring at the rotating speed of 120r/min for 20min, and standing for 20min to obtain a mixed solution.
Step 2: and adding 10% of a mixture of aminoamide and ethylene tetramine and 4.0% of polyoxyethylene ether serving as a surfactant into the mixed solution, stirring for 10min, adding 1.0% of potassium molybdate and 50% of deionized water, stirring for 1.0h, and cooling to room temperature to obtain the phosphorus-free scale and corrosion inhibitor for the heat supply network.
Example 4
A preparation method of a phosphorus-free scale and corrosion inhibitor for a heat supply network comprises the following steps:
step 1: mixing 20% of lauric acid polymer, a mixture of capric acid and epoxy succinic acid, 15% of a mixture of sodium lignosulfonate and sodium lignin humate and 5% of hydrolyzed polymaleic anhydride with the molecular weight of 200 in percentage by mass, heating to 65 ℃, stirring at the rotating speed of 160r/min for 20min, and standing for 10min to obtain a mixed solution.
Step 2: adding a mixture of 4% of dodecylamine and ethylene tetramine and 5.0% of nonylphenol polyoxyethylene ether serving as a surfactant into the mixed solution, stirring for 30min, adding 2.0% of zinc molybdate and 49% of deionized water, stirring for 1.0h, and cooling to room temperature to obtain the phosphorus-free scale and corrosion inhibitor for the heat supply network.
Example 5
A preparation method of a phosphorus-free scale and corrosion inhibitor for a heat supply network comprises the following steps:
step 1: mixing 20% of gluconic acid, a mixture of citric acid and epoxy succinic acid, 30% of a mixture of potassium lignosulfonate and sodium lignin humate and 10% of hydrolyzed polymaleic anhydride with the molecular weight of 800 by mass percentage, heating to 65 ℃, stirring at the rotating speed of 160r/min for 20min, and standing for 20min to obtain a mixed solution.
Step 2: and adding a mixture of 10% of triethanolamine and octadecylamine and 5.0% of surfactant polyoxyethylene ether into the mixed solution, stirring for 30min, adding 2.0% of zinc molybdate and 23% of deionized water, stirring for 1.0h, and cooling to 20 ℃ to obtain the phosphorus-free scale and corrosion inhibitor for the heat supply network.
Example 6
A preparation method of a phosphorus-free scale and corrosion inhibitor for a heat supply network comprises the following steps:
step 1: mixing 5% of lauric acid polymer, a mixture of dialkyl fatty acid and epoxy succinic acid, 5% of a mixture of sodium lignosulfonate and sodium lignin humate and 5% of hydrolyzed polymaleic anhydride with the molecular weight of 200 in percentage by mass, heating to 40 ℃, stirring at the rotating speed of 80r/min for 15min, and standing for 10min to obtain a mixed solution.
Step 2: adding a mixture of 2% of methoxypropylamine and decaalkylamine and 1.0% of surfactant dodecyl alcohol polyoxyethylene ether into the mixed solution, stirring for 10min, adding 0.5% of potassium molybdate and 81.5% of deionized water, stirring for 0.5h, and cooling to room temperature to obtain the heat supply network phosphorus-free scale and corrosion inhibitor.
Application example 1
Calcium carbonate scale inhibition performance test
1000ml of heat supply network make-up water (full alkalinity of 1.5mmol/L, calcium hardness of 1.4mmol/L) is taken, 10mg/L of the heat supply network non-phosphorus scale and corrosion inhibitor stock solution obtained in the embodiment 1 is added to a constant temperature water bath at 95 +/-1 ℃, the test duration is 24 hours, a cooled water sample is filtered by a filter membrane, and the concentration of scale-forming calcium ions in the filtered filtrate is measured. And (3) calculating the scale inhibition rate of the scale inhibitor on calcium carbonate, wherein the scale inhibition rate of the sample under the test condition is 95%.
Performance test of corrosion inhibition effect
According to the evaluation method of the metal corrosion rate in DB 21/T2662.5-2016, the water supplemented by a heat supply network (full alkalinity of 1.5mmol/L and calcium hardness of 1.4mmol/L) is used as test water, dynamic corrosion coupon tests are respectively carried out under the conditions of adding the scale and corrosion inhibitor and not adding the scale and corrosion inhibitor, the annual corrosion rate and corrosion inhibition rate of a test piece under the conditions of adding the medicine and not adding the medicine are calculated, and when the dosage of the scale and corrosion inhibitor is 20mg/L, the corrosion inhibition rate is 96%.
Application example 2
Calcium carbonate scale inhibition performance test
And (2) adding 20mg/L of the heat supply network non-phosphorus scale and corrosion inhibitor stock solution obtained in the embodiment 3 into 1000ml of heat supply network supplementing water (full alkalinity is 2.0mmol/L, calcium hardness is 1.6mmol/L), carrying out constant temperature water bath at 95 +/-1 ℃, testing for 24 hours, filtering a cooled water sample through a filter membrane, and measuring the concentration of scale-forming calcium ions in the filtered water. And (3) calculating the scale inhibition rate of the scale inhibitor on calcium carbonate, wherein the scale inhibition rate of the sample under the test condition is 94%.
Performance test of corrosion inhibition effect
According to the evaluation method of the metal corrosion rate in DB 21/T2662.5-2016, the water supplemented by a heat supply network (full alkalinity is 2.6mmol/L, calcium hardness is 1.6mmol/L) is used as test water, dynamic corrosion coupon tests are respectively carried out under the conditions of adding the scale and corrosion inhibitor and not adding the scale and corrosion inhibitor, the annual corrosion rate and corrosion inhibition rate of a test piece under the conditions of adding the medicine and not adding the medicine are calculated, and when the adding amount of the scale and corrosion inhibitor is 20mg/L, the corrosion inhibition rate is 96%.
Application example 3
Calcium carbonate scale inhibition performance test
And (2) adding 20mg/L of the heat supply network non-phosphorus scale and corrosion inhibitor stock solution obtained in the embodiment 5 into 1000ml of heat supply network supplementing water (full alkalinity is 2.5mmol/L, calcium hardness is 2.1mmol/L) to obtain a constant temperature water bath at 95 +/-1 ℃, testing for 24 hours, filtering a cooled water sample through a filter membrane, and measuring the concentration of scale-forming calcium ions in the filtered water. And (3) calculating the scale inhibition rate of the scale inhibitor on calcium carbonate, wherein the scale inhibition rate of the sample under the test condition is 94%.
Performance test of corrosion inhibition effect
According to the evaluation method of the metal corrosion rate in DB 21/T2662.5-2016, the water supplemented by a heat supply network (full alkalinity is 2.5mmol/L, calcium hardness is 2.1mmol/L) is used as test water, dynamic corrosion coupon tests are respectively carried out under the conditions of adding the scale and corrosion inhibitor and not adding the scale and corrosion inhibitor, the annual corrosion rate and corrosion inhibition rate of a test piece under the conditions of adding the medicine and not adding the medicine are calculated, and when the adding amount of the scale and corrosion inhibitor is 20mg/L, the corrosion inhibition rate is 98%.
Application example 4
Calcium carbonate scale inhibition performance test
1000ml of heat supply network make-up water (full alkalinity 0.5mmol/L, calcium hardness 0.4mmol/L) is taken, 10mg/L of the heat supply network non-phosphorus scale and corrosion inhibitor stock solution obtained in the embodiment 6 is added to a constant temperature water bath at 95 +/-1 ℃, the test time is 24 hours, a cooled water sample is filtered by a filter membrane, and the concentration of scale-forming calcium ions in the filtered filtrate is measured. And (3) calculating the scale inhibition rate of the scale inhibitor on calcium carbonate, wherein the scale inhibition rate of the sample under the test condition is 98%.
Performance test of corrosion inhibition effect
According to the method for evaluating the metal corrosion rate in DB 21/T2662.5-2016, the water for supplementing a heat supply network (full alkalinity of 0.5mmol/L and calcium hardness of 0.4mmol/L) is used as test water, dynamic corrosion coupon tests are respectively carried out under the conditions of adding a scale and corrosion inhibitor and not adding the scale and corrosion inhibitor, the annual corrosion rate and the corrosion inhibition rate of a test piece under the conditions of adding medicine and not adding the medicine are calculated, and when the dosage of the scale and corrosion inhibitor is 10mg/L, the corrosion inhibition rate is 92%.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A phosphorus-free scale and corrosion inhibitor for a heat supply network is characterized by comprising the following components in percentage by mass: 5.0-20.0% of organic carboxylic acid mixture, 5.0-30.0% of lignin derivative, 5.0-10.0% of hydrolyzed polymaleic anhydride, 2.0-10.0% of organic amine mixture, 1.0-5.0% of surfactant, 0.5-2.0% of molybdate and the balance of deionized water.
2. The phosphorus-free scale and corrosion inhibitor for the heat supply network of claim 1, wherein the organic carboxylic acid mixture is one or more of citric acid, gluconic acid, lauric acid polymer, dialkyl fatty carboxylic acid, capric acid, epoxy succinic acid and epoxy succinic acid; the organic carboxylic acid mixture is a mono-or poly-organic carboxylic acid mixture with 2-14 carbon atoms.
3. The phosphorus-free scale and corrosion inhibitor for the heat supply network according to claim 1, wherein the lignin derivative is one or more of sodium lignosulfonate, potassium lignosulfonate, ammonium lignosulfonate, sodium lignosulfonate and potassium lignosulfonate.
4. The phosphorus-free scale and corrosion inhibitor for heat supply networks as claimed in claim 1, wherein the molecular weight of the hydrolyzed polymaleic anhydride is 200-800.
5. The phosphorus-free scale and corrosion inhibitor for heat supply networks according to claim 1, wherein the organic amine mixture is one or more of triethanolamine, methyl tertiary amine, methoxypropylamine, aminoamide, ethylene tetramine and dodecylamine.
6. The phosphorus-free scale and corrosion inhibitor for heat supply networks according to claim 1, wherein the surfactant is one or more of polyoxyethylene ether, lauryl fatty alcohol polyoxyethylene ether and nonylphenol polyoxyethylene ether.
7. The phosphorus-free scale and corrosion inhibitor for heat supply networks according to claim 1, wherein the molybdate is one or more of ammonium molybdate, potassium molybdate, sodium molybdate and zinc molybdate.
8. The preparation method of the phosphorus-free scale and corrosion inhibitor for the heat supply network of any one of claims 1 to 7, which is characterized by comprising the following steps:
step 1: mixing an organic carboxylic acid mixture, a lignin derivative and hydrolyzed polymaleic anhydride, heating, uniformly stirring, and standing to obtain a mixed solution;
step 2: and adding the organic amine mixture and the surfactant into the mixed solution, stirring, adding molybdate and deionized water, and stirring and cooling to obtain the phosphorus-free scale and corrosion inhibitor for the heat supply network.
9. The preparation method of the phosphorus-free scale and corrosion inhibitor for the heat supply network according to claim 8, wherein in the step 1, the heating is carried out to 40-65 ℃, the stirring speed is 80-160r/min, the stirring time is 15-20 min, and the standing time is 10-20 min; in the step 2, adding an organic amine mixture and a surfactant into the mixed solution, and stirring for 10-30 min; adding molybdate and deionized water, and stirring for 0.5-l.0h; stirring and cooling to room temperature.
10. The application of the phosphorus-free scale and corrosion inhibitor for the heat supply network in removing the corrosion dirt of the heat supply network system according to any one of claims 1 to 7.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116550152A (en) * | 2023-05-17 | 2023-08-08 | 杭州上拓环境科技股份有限公司 | Low-content high-efficiency reverse osmosis membrane scale inhibitor and preparation process thereof |
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