CN100441657C - Cooling fluid of engine - Google Patents

Cooling fluid of engine Download PDF

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CN100441657C
CN100441657C CNB2006100873592A CN200610087359A CN100441657C CN 100441657 C CN100441657 C CN 100441657C CN B2006100873592 A CNB2006100873592 A CN B2006100873592A CN 200610087359 A CN200610087359 A CN 200610087359A CN 100441657 C CN100441657 C CN 100441657C
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acid
molybdate
carboxylic acid
engine coolant
alkali metal
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CN1872944A (en
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白剑利
王双田
邱雪梅
吴卫明
刘学丰
郭茂兴
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Beijing Bluestar Cleaning Co Ltd
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BLUE STAR ENVIRONMENTAL ENGINEERING Co Ltd
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Abstract

The present invention discloses cooling fluid of an engine, which is composed of ethylene glycol, fatty carboxylic acid and alkali metal salt thereof, polytricarboxylic acid, sodium benzoate, sodium tetraborate decahydrate, molybdate, sodium silicate, a silicate stabilizer, an azole compound, a defoaming agent and deionized water. The cooling fluid of an engine of the present invention does not comprise substances with large toxicity and strong pollution, such as amine substances, nitrite, phosphate, imidazole, etc. The present invention can effectively prevent all the contacted metal materials and non-metal materials in an engine cooling system from being corroded. In particular, the present invention has favorable inhibiting action on the corrosion of soldering tin, aluminum and alloy thereof, no gel, no sedimentation formation, and stability in the variation ranges of relatively low concentration and large pH value.

Description

Engine coolant
Technical field
The present invention relates to a kind of engine coolant, belong to the chemical composition technical field.
Technical background
Water uses as the engine coolant of motor car engine always.But the freezing point height, when temperature was lower than 0 ℃, water freezing increased volume, causes water tank or the spalling of cooling system pipeline easily; Be dissolved in metallic salt in the water back that is heated and form incrustation scale, reduce heat transfer efficiency; Water also can cause the metallic corrosion of engine-cooling system.People adopt the aqueous solution (as calcium chloride, magnesium chloride, SODIUMNITRATE, Sodium Nitrite) of salt can reduce freezing point to below-30 ℃, but can not solve the metallic corrosion problem.Afterwards, it is found that the performance of aqueous glycol solution is good, freezing point can reach below-60 ℃ when certain ratio, and boiling point is more than 110 ℃, and it can not damage rubber hose, adds behind the rust-preventive agent not corroding metal, and price is relatively cheap, does not have bad smell.Therefore this liquid extensively adopts the frostproofer as the engine coolant of automobile cooling system at present.
The additive formulations technology is the core of engine coolant technology.
Because silicate is the special corrosion inhibitor of aluminium and aluminium alloy,, the good corrosionproof protection of aluminium is become both at home and abroad research emphasis to automobile engine cooling liquid along with the widespread use of aluminium alloy at car engine cooling system.Simultaneously, the chemical substance that contains harm environment such as amine substance, nitrite, phosphoric acid salt, imidazoles and human health in not wishing to fill a prescription.Conventional inorganic silicate is that antifreeze formulations is arisen at the historic moment, but because the silicate instability, gel is separated out and is formed precipitation easily, and use is restricted.
External in order to solve the problem of this respect, brought into use full organic acid type to send out engine coolant.And full organic acid type engine coolant is because the production cost height, and easily produces cavitation corrosion and use and be subjected to certain limitation.
Summary of the invention
The present invention is exactly on the basis of conventional silicate-type and full organic acid type engine coolant technology, has introduced organic carboxyl acid, and the especially introducing of organic ternary poly carboxylic acid has improved the correlated performance of cooling fluid greatly.
Set out in the theory of the chemisorption process of metallic surface according to the organic inhibition agent molecule, infer that carboxyl is many more, molecule is big more, and easy more formation adsorption film and adsorption film are thick more, and be better to the all-round protection effect of metal.The present invention proposes the application of ternary polycarboxylate especially; with metal better all-round protection effect is arranged than engine-cooling systems such as monobasic or di-carboxylic acid salt pair aluminiums; greatly reduce the spot corrosion of engine coolant, improved inhibition protective value cavitation corrosion to engine-cooling system.Its prescription is as follows:
Raw material weight percentage ratio
Ethylene glycol 30~96%
Aliphatic carboxylic acid and an alkali metal salt 0.1~3.5% thereof
Polymerization tribasic carboxylic acid 0.1~1.0%
Sodium Benzoate 0.1~2.5%
Sodium borate decahydrate 0.01~1.5%
Molybdate 0.01~0.5%
Water glass 0.1~0.5%
Silicate stabilizers 0.1~0.5%
Azole compounds 0.01~0.35%
Defoamer 0.001~0.2%
The deionized water surplus
Described polymerization tribasic carboxylic acid, it is characterized by on 1,3,5 of triazine ring respectively has an organic poly carboxylic acid base, and its molecular structural formula is:
Figure C20061008735900051
Wherein: polymerization degree n is 3~8.
Be to be synthesized into by trimeric cyanamide and the addition of direct steel lipid acid, it is 5 that the product n value of representative is arranged most, as the product L190 of Switzerland vapour Bagong department good effect is just arranged.
Binary of selecting for use and tribasic carboxylic acid additive can reduce the ethylene glycol cooling fluid to corrosion of metal, and can strengthen the stability of silicate, improve the work-ing life of cooling fluid.
Described monocarboxylic acid additive can reduce cavitation erosion and the spot corrosion of ethylene glycol cooling fluid to metal.
Described lipid acid and an alkali metal salt thereof, from caproic acid, enanthic acid, sad, isocaprylic acid, n-nonanoic acid, capric acid, neodecanoic acid, undecanoic acid, dodecylic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid and an alkali metal salt thereof, select, comprise one or more mixture.Wherein especially with isocaprylic acid, sebacic acid first-selection.
Described molybdate can reduce the corrosion of ethylene glycol cooling fluid to cast aluminium alloy scatterer and cylinder cap, prevents aluminium pump cavitation corrosion.Being to select from Sodium orthomolybdate, potassium molybdate, ammonium molybdate, lithium molybdate, is first-selection with Sodium orthomolybdate, potassium molybdate especially.
Azole compounds that the present invention selects for use and molybdate synergy make cooling liquid formulation can use the molybdate of lower concentration effectively to reduce corrosion.
Azole compounds comprises benzotriazole, tolyltriazole, mercapto benzothiazole, first-selected benzotriazole, tolyltriazole.
Described water glass comprises Starso, sodium metasilicate, and wherein Starso comprises 5 water sodium metasilicates and 9 water sodium metasilicates, first-selected 9 water sodium metasilicates.
Described silicate stabilizers can effectively suppress the gel of silicate, improves the corrosion inhibition performance of whole prescription, and cooling fluid does not produce gel or precipitation in dilution or use.Adopt siloxanes or its phosphate compounds.
Described defoamer is the mixture of block polyether and ester thereof.
The Sodium Benzoate that the present invention selects for use can effectively reduce the corrosion of cast iron, steel, copper.
The present invention uses sodium borate decahydrate as the pH value buffer reagent, and its surge capability is extremely strong, thereby helps the control of pH value, and is also effective in bigger pH variation range, also can effectively improve the reserve alkalinity of cooling fluid simultaneously.
The preparation method of engine coolant of the present invention: according to each amount of substance of prescription regulation, get in an amount of ethylene glycol, the deionized water input reactor, stirred at normal temperatures 10 minutes, and then get an amount of aliphatic carboxylic acid and an alkali metal salt thereof, polymerization tribasic carboxylic acid, Sodium Benzoate, sodium borate decahydrate, molybdate, azole compounds adds in the reactor successively, stirs after 30 minutes; Add silicate stabilizers, stirs and add water glass and defoamer again after 10 minutes, get final product until dissolving fully.
Adopt the engine coolant of the present invention's prescription not contain the materials that toxicity is big, contaminative is strong such as amine substance, nitrite, phosphoric acid salt, imidazoles; Selected organic carboxylate, azole, molybdate, borate, silicate are combined; has the synergistic slow corrosion effect between each material; can effectively prevent interior all metals that contacted of engine-cooling system and the corrosion of non-metallic material, particularly the corrosion that prevents scolding tin, aluminium and alloy thereof be had the good restraining provide protection.Gel do not occur or form precipitation, and stable in relatively low concentration and bigger pH variation range.
The selected organic acid of the present invention can strengthen the stability of silicate; and the inhibiter of inorganic salt type mainly is by making the metallic surface that passivation take place to the protection of metallic surface; generate passive film; its spending rate is very fast; and organic acid mainly is by in the metallic surface absorption film-forming to the protection of metal; change its surperficial electrochemical properties, its spending rate is slower.Prescription of the present invention combines inorganic salt and organic acid characteristics, forms the synergetic property composite protection film, long service life.
The present invention utilizes the synergy of inorganic inhibitor and organic inhibitor, reduces the usage quantity of organic inhibitor greatly, than full organic acid type cooling fluid bigger cost advantage is arranged.
Embodiment
Cooling liquid formulation of the present invention is through a large amount of screening experiments, obtained the formula combination of economical rationality, technology excellence.Following table is 8 Example formulations:
Table 1 Example formulations
Figure C20061008735900071
Figure C20061008735900081
Engine coolant performance index data of the present invention see Table 2.
Table 2 performance index
Figure C20061008735900082
Figure C20061008735900091
In order to prove that engine coolant of the present invention is better than conventional inorganic salt type cooling fluid and full organic acid type cooling fluid to metal protection, three kinds of cooling fluids have been carried out the contrast corrosion test, the corrosion contrast and experiment sees Table 3.
Table 3 contrast experiment data
Figure C20061008735900092
From the data of table 2, table 3 as can be seen, the cooling fluid of the technology of the present invention preparation, the not only complete conformance with standard requirements of physical and chemical index such as density, boiling point, freezing point, ash content, pH value, moisture, reserve alkalinity, cl content.And, have quite good foam tendency owing to add special defoamer.Of paramount importance is that cooling fluid of the present invention has excellent corrosion inhibition provide protection to engine-cooling systems such as red copper, brass, scolding tin, carbon steel, cast aluminium, cast irons with metal; test piece weightlessness is well below standard-required, and is the most outstanding to the protection of cast aluminium and scolding tin.Particularly the result of cast aluminium alloy heat transfer corrosion test and aluminium pump cavitation corrosion test is outstanding.

Claims (5)

1. an engine coolant is characterized in that, forms through mixing by following prescription:
Raw material weight percentage ratio
Ethylene glycol 30~96%
Aliphatic carboxylic acid and an alkali metal salt 0.1~3.5% thereof
Polymerization tribasic carboxylic acid 0.1~1.0%
Sodium Benzoate 0.1~2.5%
Sodium borate decahydrate 0.01~1.5%
Molybdate 0.01~0.5%
Water glass 0.1~0.5%
Silicate stabilizers 0.1~0.5%
Azole compounds 0.01~0.35%
Defoamer 0.001~0.2%
The deionized water surplus
Described polymerization tribasic carboxylic acid is on 1,3,5 of triazine ring an organic poly carboxylic acid base to be arranged respectively, and its molecular structural formula is:
Figure C2006100873590002C1
Wherein: polymerization degree n is 3~8;
Described azole compounds is selected from: benzotriazole, tolyltriazole, mercapto benzothiazole;
Described aliphatic carboxylic acid and an alkali metal salt thereof are selected from one or more in the following material: caproic acid, enanthic acid, sad, isocaprylic acid, n-nonanoic acid, capric acid, neodecanoic acid, undecanoic acid, dodecylic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid and an alkali metal salt thereof;
Described silicate stabilizers is siloxanes or its phosphate compounds.
2. according to the engine coolant of claim 1, it is characterized in that described aliphatic carboxylic acid and an alkali metal salt thereof are selected from the following material one or more: isocaprylic acid, sebacic acid and their an alkali metal salt.
3. according to the engine coolant of claim 1, it is characterized in that described molybdate is selected from: Sodium orthomolybdate, potassium molybdate, ammonium molybdate, lithium molybdate.
4. according to the engine coolant of claim 3, it is characterized in that described molybdate is Sodium orthomolybdate, potassium molybdate.
5. according to the engine coolant of claim 1, it is characterized in that described defoamer is the mixture of block polyether and ester thereof.
CNB2006100873592A 2006-06-12 2006-06-12 Cooling fluid of engine Active CN100441657C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111548774A (en) * 2020-05-14 2020-08-18 广研德孚科技发展(深圳)有限公司 Cooling liquid for plug-in hybrid electric vehicle and preparation process thereof

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CN101514458B (en) * 2007-11-27 2011-04-20 北京科技大学 Inhibitor in aqueous heat exchange medium for La-Fe-Si series room temperature magnetic refrigeration materials
US20100270494A1 (en) * 2009-04-22 2010-10-28 Chevron U.S.A. Inc. Hot test fluid containing vapor phase inhibition
CN101955755B (en) * 2009-07-20 2013-07-24 比亚迪股份有限公司 Engine coolant
CN101691484B (en) * 2009-09-19 2011-07-20 核工业二〇三研究所技术开发部 Engine antifreezing solution
CN102286270B (en) * 2010-06-19 2014-04-30 比亚迪股份有限公司 Engine cooling liquid and preparation method thereof
CN102453469B (en) * 2010-10-26 2014-05-28 比亚迪股份有限公司 Engine coolant and preparation method thereof
CN102363725A (en) * 2010-12-14 2012-02-29 深圳车仆汽车用品发展有限公司 Organic-inorganic composite type engine coolant
CN103059820B (en) * 2011-10-19 2016-01-13 中国石油化工股份有限公司 A kind of non-aqueous coolant for engine composition
CN103059819B (en) * 2011-10-19 2015-08-26 中国石油化工股份有限公司 A kind of non-aqueous coolant for engine composition
CN102424962B (en) * 2011-12-28 2014-12-10 上海中孚特种油品有限公司 Corrosion inhibitor for copper and copper alloy, and preparation method thereof
BR112015018314B1 (en) * 2013-02-13 2021-12-28 Basf Se ANTIFREEZE CONCENTRATE WITH CORROSION PROTECTION, AQUEOUS REFRIGERANT COMPOSITION, USES OF AN AQUEOUS REFRIGERANT COMPOSITION AND A COMPOUND, AND, METHOD FOR REDUCING ALUMINUM HYDROXIDE GEL PRECIPITATION
CN104250544B (en) * 2013-06-25 2017-04-19 中国石油化工股份有限公司 Antifreeze fluid for coal-mine hydraulic supports
CN104419385B (en) * 2013-09-10 2017-11-14 中国石油化工股份有限公司 A kind of Condition of Engine Coolant for Heavy Duty Engines and preparation method thereof
CN103666403A (en) * 2013-12-02 2014-03-26 青岛康普顿科技股份有限公司 Vehicle engine cooling liquid
CN103666404B (en) * 2013-12-26 2017-01-04 北京蓝星清洗有限公司 A kind of full stress-strain hard water stable type engine coolant and preparation method thereof
CN103756649B (en) * 2014-02-19 2016-08-31 日出东方太阳能股份有限公司 A kind of anti-icing fluid for solar water heater and preparation method thereof
CN106634867A (en) * 2016-12-05 2017-05-10 钦州市钦南区生产力促进中心 Engine coolant and preparation method thereof
CN107384334A (en) * 2017-06-30 2017-11-24 颍上北方动力新能源有限公司 A kind of coating machine condensing agent
CN109666459B (en) * 2017-10-16 2021-01-15 中国石油化工股份有限公司 High-temperature-resistant long-life engine coolant
CN109666458A (en) * 2017-10-17 2019-04-23 中国石油化工股份有限公司 A kind of siliceous organic engine cooling liquid and its application
CN109837071B (en) * 2017-11-24 2021-03-23 北京蓝星清洗有限公司 Cooling liquid for wind generating set and preparation method thereof
CN112574721A (en) * 2020-11-19 2021-03-30 江苏艾德露环保科技有限公司 Multi-effect environment-friendly glycol type automobile cooling liquid and preparation method thereof
CN112745808A (en) * 2021-01-19 2021-05-04 广东石油化工学院 Heat management system liquid and preparation method thereof
CN112745809A (en) * 2021-01-20 2021-05-04 广东石油化工学院 Low-conductivity cooling liquid and preparation method thereof
CN115820225A (en) * 2022-11-21 2023-03-21 中国重汽集团济南动力有限公司 Engine coolant with long service life and excellent corrosion resistance under long service life

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