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CN112574720B - Low-temperature heat transfer medium with function of inhibiting deposit formation and preparation method and application thereof - Google Patents

Low-temperature heat transfer medium with function of inhibiting deposit formation and preparation method and application thereof Download PDF

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CN112574720B
CN112574720B CN201910943724.2A CN201910943724A CN112574720B CN 112574720 B CN112574720 B CN 112574720B CN 201910943724 A CN201910943724 A CN 201910943724A CN 112574720 B CN112574720 B CN 112574720B
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heat transfer
temperature heat
low
transfer medium
corrosion inhibitor
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CN112574720A (en
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冯会良
龙茵
张凯蛟
赵海鹏
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
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Abstract

The invention relates to the technical field of low-temperature heat transfer media, in particular to a low-temperature heat transfer medium with a function of inhibiting the formation of deposits, and a preparation method and application thereof. The invention provides a low-temperature heat transfer medium with a function of inhibiting deposit formation, which comprises the following components: water-soluble alcohol, organic acid corrosion inhibitor, triazole corrosion inhibitor, dispersant, pH regulator and defoaming agent. The low-temperature heat transfer medium adopts a composite corrosion inhibitor formed by compounding an organic carboxylic acid corrosion inhibitor and a triazole corrosion inhibitor, and provides excellent anti-corrosion protection for red copper, brass, steel, iron, cast aluminum, soldering tin and other metals in a heat transfer system; meanwhile, the composite material has excellent performance of inhibiting the formation and adsorption of sediments, avoids the sediments from blocking a cooling system, is beneficial to maintaining the normal operation of the cooling system and prolongs the service life of a low-temperature heat transfer medium; and the paint does not contain inorganic salt components such as borax, molybdate, nitrite, phosphate and the like and organic amine, and has small harm to the environment and human body.

Description

Low-temperature heat transfer medium with function of inhibiting deposit formation and preparation method and application thereof
Technical Field
The invention relates to the technical field of low-temperature heat transfer media, in particular to a low-temperature heat transfer medium with a function of inhibiting the formation of deposits, and a preparation method and application thereof.
Background
The low-temperature heat transfer medium is generally composed of functional additives such as a small molecular alcohol antifreezing agent, a water-miscible compound corrosion inhibitor, a defoaming agent and a coloring agent, has the advantages of good antifreezing property, high boiling point, low corrosivity and the like compared with pure water as a heat transfer medium, and is generally used in water-cooling systems of equipment such as central air conditioners, internal combustion engines, split solar water heaters, power electronic device converters and the like.
When in use, the low-temperature heat transfer medium is in contact with metal materials such as steel, cast iron, solder, red copper, brass, cast aluminum and the like in a water cooling system, and various corrosion forms such as electrochemical corrosion, pitting corrosion, crevice corrosion and the like exist. In the prior art, borax, phosphate, silicate, chromate, organic amine, organic acid and other corrosion inhibitors are added into a low-temperature heat transfer medium to inhibit the corrosion of metals in a heat transfer system. The organic acid corrosion inhibitor is gradually used as a corrosion inhibitor mainly used for low-temperature heat transfer media such as engine cooling liquid and the like due to the advantages of small harm to the environment, low degradation rate, long service life and the like, however, in the long-term use process, due to self degradation, crystallization, adsorption, interaction with calcium, magnesium and various metal corrosive ions and the like, deposits with complex components are formed in a cooling system and are adsorbed on parts such as a radiator pipeline, a water-cooling substrate, a filter and the like, so that the local blockage of the cooling system is caused, the flow of the heat transfer media is reduced, and the temperature rise of the system is too fast. Therefore, it is of great importance to develop a low-temperature heat transfer medium having a function of suppressing the formation of deposits.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a low-temperature heat transfer medium which has a good anti-corrosion effect on various metals, has little environmental pollution and has the function of efficiently inhibiting the formation of deposits, and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a low-temperature heat transfer medium with a function of inhibiting deposit formation, which comprises the following components: antifreeze, corrosion inhibitor and dispersant; the corrosion inhibitor comprises an organic acid corrosion inhibitor and a triazole corrosion inhibitor; the dispersant comprises an amphiphilic high molecular polymer.
In order to improve the corrosion resistance of the low-temperature heat transfer medium, in the prior art, the corrosion inhibitor in the low-temperature heat transfer medium mostly contains borax, molybdate, nitrite, phosphate, organic amine and other substances, and the substances have good corrosion inhibition performance but have great harm to the environment and human body. When screening corrosion inhibitors which have less environmental pollution and excellent corrosion resistance, the invention finds that a plurality of corrosion inhibition components are environment-friendly, but have limited corrosion inhibition function, particularly have poor corrosion inhibition function effect on easily-corroded metals, and can hardly achieve better effect even if the corrosion inhibitors are compounded or the dosage is increased. However, the organic acid corrosion inhibitor is easy to form deposits in the using process, and the invention discovers that the formation of the deposits can be accelerated after the organic acid corrosion inhibitor is compounded with the triazole corrosion inhibitor, and the amphiphilic high molecular polymer is introduced to play a better dispersing role and effectively inhibit the formation of the deposits.
The corrosion inhibitor provided by the invention can only consist of an organic acid corrosion inhibitor and a triazole corrosion inhibitor.
Preferably, the organic acid corrosion inhibitor is one or more selected from monocarboxylic acid with 5-10 carbon atoms, dicarboxylic acid with 4-12 carbon atoms, benzoic acid, substituted acid thereof and alkali metal salt thereof. The triazole corrosion inhibitor is one or two of benzotriazole and methylbenzotriazole.
Specifically, the monocarboxylic acid with 5-10 carbon atoms is one or more selected from valeric acid, caproic acid, heptanoic acid, caprylic acid, isooctanoic acid, pelargonic acid, isononanoic acid and capric acid. The dicarboxylic acid with 4-12 carbon atoms is one or more selected from succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid. The substituted acid of the benzoic acid is one or more selected from o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, o-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, o-methoxybenzoic acid, m-methoxybenzoic acid, p-methylbenzoic acid, p-tert-butylbenzoic acid, phthalic acid and terephthalic acid.
More preferably, the organic acid corrosion inhibitor is a mixture of one selected from monocarboxylic acids with 6-10 carbon atoms, one selected from dicarboxylic acids with 6-10 carbon atoms and substituted acids of benzoic acid.
Preferably, the mass ratio of the organic acid corrosion inhibitor to the triazole corrosion inhibitor is (25-50): 1.
in the present invention, the antifreezing agent is preferably a water-soluble alcohol.
Preferably, the water-soluble alcohol is one or a mixture of more of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and glycerol. More preferably ethylene glycol and/or propylene glycol.
The invention discovers that amphiphilic high molecular polymer formed by copolymerizing hydrophilic monomer acrylic acid, maleic acid or derivatives thereof, hydrophobic monomer acrylic ester and styrene is introduced into a compound system of the water-soluble alcohol and the specific organic acid corrosion inhibitor and the triazole corrosion inhibitor, the amphiphilic high molecular polymer can be strongly adsorbed on the surface of granular water-insoluble substances, excellent wetting and dispersibility are shown, the components can be better coordinated and matched, and the formation of sediments can be more effectively inhibited.
Preferably, the high molecular polymer is a copolymer formed by one selected from hydrophilic polymerization monomers of acrylic acid, methacrylic acid, maleic acid and maleic anhydride and one selected from hydrophobic polymer monomers of acrylic ester and styrene.
More preferably, the organic acid corrosion inhibitor is a mixture of isooctanoic acid, sebacic acid and p-tert-butyl benzoic acid; the dispersant comprises a copolymer of an acrylic monomer and an acrylate monomer. By adopting the compounding way of the specific corrosion inhibitor and the dispersant, the corrosion inhibitor has better performance of preventing corrosion of various metals and inhibiting formation of sediments.
The molecular weight of the copolymer formed by the acrylic monomer and the acrylate monomer is preferably 2000-20000.
Preferably, the low-temperature heat transfer medium comprises the following components in parts by weight:
Figure BDA0002223625620000041
more preferably, the low-temperature heat transfer medium comprises the following components in parts by weight:
Figure BDA0002223625620000042
the dispersant comprises a copolymer of an acrylic monomer and an acrylate monomer.
The molecular weight of the copolymer formed by the acrylic monomer and the acrylic ester monomer is preferably 2000-20000.
The low-temperature heat transfer medium can be further added with a pH regulator and a defoaming agent.
Preferably, the low-temperature heat transfer medium comprises the following components in parts by weight:
Figure BDA0002223625620000043
more preferably, the low-temperature heat transfer medium comprises the following components in parts by weight:
Figure BDA0002223625620000044
Figure BDA0002223625620000051
the pH regulator is preferably an alkaline pH regulator, such as NaOH, KOH and the like; the dosage of the pH regulator is used for regulating the pH of the low-temperature heat transfer medium to 7.5-9.0. The various metals in the heat transfer system can be better protected within the above pH range.
The defoaming agent is preferably polyether modified polysiloxane.
As a preferable scheme of the invention, the low-temperature heat transfer medium comprises the following components in parts by weight based on 100 parts of the total weight:
Figure BDA0002223625620000052
and the amount of NaOH or KOH is used for adjusting the pH value of the low-temperature heat transfer medium to 7.5-9.0.
The above-described preferred conditions may be combined with each other to obtain a preferred embodiment of the present invention, on the basis of general knowledge in the art.
The low-temperature heat transfer medium provided by the invention has an excellent anti-corrosion effect on various metals, can effectively inhibit the formation, adsorption and accumulation of sediments in the use process, avoids the reduction of heat transfer capacity of a cooling system caused by sediment blockage, ensures the normal operation of the cooling system and the service life of the low-temperature heat transfer medium, can be widely applied to water-cooling systems of equipment such as central air conditioners, internal combustion engines, split solar water heaters, power electronic device converters and the like, and is particularly suitable for engine cooling systems.
The low temperature heat transfer medium may be prepared by methods conventional in the art, for example: the components are mixed evenly according to the proportion.
The invention also provides a preparation method of the low-temperature heat transfer medium, which comprises the following steps: mixing an antifreezing agent, an organic acid corrosion inhibitor, a triazole corrosion inhibitor, a dispersing agent, a pH regulator and a defoaming agent according to a mass ratio.
The invention also provides the application of the low-temperature heat transfer medium in water-cooling systems of central air conditioners, internal combustion engines, split solar water heaters and converters of power electronic devices.
The invention has the beneficial effects that: the low-temperature heat transfer medium provided by the invention has the following advantages:
(1) the device has the functions of efficiently inhibiting generation, adsorption and accumulation of sediments, can effectively avoid the reduction of heat transfer capacity of a heat dissipation system caused by sediment blockage, and ensures the normal operation of a cooling system and the longer service life of a low-temperature heat transfer medium;
(2) the corrosion-resistant antirust paint has excellent corrosion-resistant and antirust functions on various metals such as copper, steel, cast iron, soldering tin, cast aluminum and the like, and can effectively inhibit the corrosion and the rusting of the metals in a cooling system;
(3) does not contain borax, molybdate, nitrite, phosphate, organic amine and other substances harmful to the environment and human bodies.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified, wherein the dispersant Acumer 6600 is a Dow chemical; dispersant T-225 and dispersant TH-1100 were purchased from Shandongtai and Water treatment science and technology Co., Ltd; defoamer HP710 was purchased from allied celebration additives trade (shanghai) ltd.
Example 1
The embodiment provides a low-temperature heat transfer medium with the function of inhibiting the formation of deposits, which comprises the following components in percentage by mass:
Figure BDA0002223625620000071
the pH was 8.1.
The preparation method of the low-temperature heat transfer medium comprises the following steps: mixing the components in proportion, and stirring uniformly to obtain the final product.
Example 2
The embodiment provides a low-temperature heat transfer medium with the function of inhibiting the formation of deposits, which comprises the following components in percentage by mass:
Figure BDA0002223625620000072
Figure BDA0002223625620000081
the pH was 8.0.
The preparation method of the low-temperature heat transfer medium comprises the following steps: mixing the components in proportion, and stirring uniformly to obtain the final product.
Example 3
The embodiment provides a low-temperature heat transfer medium with the function of inhibiting the formation of deposits, which comprises the following components in percentage by mass:
Figure BDA0002223625620000082
the pH was 8.0.
The preparation method of the low-temperature heat transfer medium comprises the following steps: mixing the components in proportion, and stirring uniformly to obtain the final product.
Example 4
The embodiment provides a low-temperature heat transfer medium with the function of inhibiting the formation of deposits, which comprises the following components in percentage by mass:
Figure BDA0002223625620000083
Figure BDA0002223625620000091
the pH was 8.0.
The preparation method of the low-temperature heat transfer medium comprises the following steps: mixing the components in proportion, and stirring uniformly to obtain the final product.
Comparative example 1
The comparative example provides a low-temperature heat transfer medium which comprises the following components in percentage by mass:
Figure BDA0002223625620000092
the pH was 8.0.
The preparation method of the low-temperature heat transfer medium comprises the following steps: mixing the components in proportion, and stirring uniformly to obtain the final product.
Comparative example 2
The comparative example provides a low-temperature heat transfer medium which comprises the following components in percentage by mass:
Figure BDA0002223625620000101
the pH was 8.0.
The preparation method of the low-temperature heat transfer medium comprises the following steps: mixing the components in proportion, and stirring uniformly to obtain the final product.
Comparative example 3
The comparative example provides a low-temperature heat transfer medium which comprises the following components in percentage by mass:
Figure BDA0002223625620000102
the pH was 8.1.
The preparation method of the low-temperature heat transfer medium comprises the following steps: mixing the components in proportion, and stirring uniformly to obtain the final product.
Comparative example 4
The comparative example provides a low-temperature heat transfer medium which comprises the following components in percentage by mass:
Figure BDA0002223625620000111
the pH was 8.1.
The preparation method of the low-temperature heat transfer medium comprises the following steps: mixing the components in proportion, and stirring uniformly to obtain the final product.
Experimental example 1: glassware corrosion test
The protective performance of the low-temperature heat transfer medium in the embodiments 1 to 4 and the comparative examples 1 to 4 of the invention on metal materials was examined by using an SH/T0085 glassware corrosion method, and the results are shown in Table 1. The glassware corrosion test results show that the low-temperature heat transfer medium of the embodiments 1 to 4 has excellent corrosion inhibition performance on red copper, brass, steel, cast iron, soldering tin, cast aluminum and other metals, and can effectively protect metal parts in a heat transfer system. The metal protection performance of the low-temperature heat transfer medium of the comparative examples 1 to 3 is equivalent to that of the examples 1 to 4, and the low-temperature heat transfer medium of the comparative example 4 has obvious corrosion to cast iron, soldering tin and cast aluminum.
TABLE 1 glassware corrosion (88. + -. 2 ℃, 336h)
Figure BDA0002223625620000112
Figure BDA0002223625620000121
Experimental example 2: analysis of deposit formation inhibiting Properties
The specific method for carrying out the comparative test on the performance of inhibiting the formation of the deposit on the low-temperature heat transfer medium in the embodiments 1 to 4 and the comparative examples 1 to 4 of the invention is as follows:
the aluminum flat tube (with the width of 16mm, the thickness of 0.2mm and the height of 2mm) of the pipe-belt type radiator for the automobile is cut into an aluminum flat tube test piece with the length of 50mm, and a hole with the diameter of 7mm is drilled in the center of the cut aluminum flat tube test piece.
The test adopts SH/T0088 engine coolant to simulate the use corrosion determination method, a metal test piece specified in SH/T0088 is not installed in the test, the manufactured flat aluminum tube test piece is assembled on a brass screw sleeved with a polytetrafluoroethylene tube, the test piece and a brass bracket are separated by an insulating washer, the test time is changed into continuous operation for two weeks, and the middle part is not stopped.
And unloading the aluminum flat tube test piece after shutdown, and observing the condition of the deposits in the test piece pipeline.
The test results are shown in table 2, and the results show that no deposit is formed in the aluminum flat tube test piece pipelines using the low-temperature heat transfer media of examples 1 to 4, and that the low-temperature heat transfer media of examples 1 to 4 have excellent dispersibility, can effectively inhibit the generation of deposits in the use process of the low-temperature heat transfer media, and avoid the blockage of heat dissipation pipelines and the reduction of heat transfer capacity. By using the low-temperature heat transfer media of comparative examples 1, 2 and 3, the test piece pipes had significant deposit accumulation, which further affected the heat transfer performance of the low-temperature heat transfer media.
TABLE 2 comparative test for deposit formation inhibiting properties
Figure BDA0002223625620000122
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (4)

1. A low-temperature heat transfer medium having a function of suppressing deposit formation, characterized by comprising the following components:
Figure FDA0003288222350000011
2. the low temperature heat transfer medium of claim 1, wherein the pH adjuster is an alkaline pH adjuster; the defoaming agent is polyether modified polysiloxane.
3. The method for producing a low-temperature heat transfer medium according to claim 1 or 2, comprising: mixing an antifreezing agent, an organic acid corrosion inhibitor, a triazole corrosion inhibitor, a dispersing agent, a pH regulator and a defoaming agent according to a mass ratio.
4. Use of the low temperature heat transfer medium of claim 1 or 2 in a water cooled cooling system of a central air conditioner, an internal combustion engine, a split solar water heater or a power electronics converter.
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