CN101717619A - Industrial low-temperature heat exchange secondary refrigerant - Google Patents
Industrial low-temperature heat exchange secondary refrigerant Download PDFInfo
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- CN101717619A CN101717619A CN200910193902A CN200910193902A CN101717619A CN 101717619 A CN101717619 A CN 101717619A CN 200910193902 A CN200910193902 A CN 200910193902A CN 200910193902 A CN200910193902 A CN 200910193902A CN 101717619 A CN101717619 A CN 101717619A
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- heat exchange
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Abstract
The invention relates to an industrial low-temperature heat exchange secondary refrigerant. The heat exchange refrigerant is used as a secondary refrigerant in chemical pharmacy of the industrial production field and an indirect heat exchange system in a biological fermentation process. The low-temperature heat exchange secondary refrigerant consists of 5 to 90 weight percent of water, 5 to 90 weight percent of C1-C4 organic alcohol, 0.5 to 2 weight percent of functional additive and the like. The low-temperature heat exchange secondary refrigerant has remarkable effects of refrigeration, corrosion prevention, bacteria inhibition, algae removal and the like; a firm passivation layer can be formed on the inner metal (iron, copper, aluminum and alloy) surface of a cooling system to effectively prevent the corrosion of environments to the cooling system; both the new and old system can use the low-temperature heat exchange secondary refrigerant; the problem that the conventional secondary refrigerant has serious corrosion to the cooling system equipment is radically solved; the safe and steady operation of the cooling system is ensured, and the operation cycle of the equipment is effectively prolonged; and the applicable range of temperature is between 80 DEG C below zero and 120 DEG C.
Description
Technical field
The invention belongs to industrial low-temperature heat exchange secondary refrigerant field, be specifically related to do the secondary refrigerant use technology in biological chemistry pharmacy in the industrial production field and the indirect heat exchange system in the biological fermentation process.
Background technology
Brewage at food; the production process and the temperature in many industrial production fields such as biological chemistry pharmacy and chemical industry are closely related; the exothermal reaction process that under lower temperature, carries out at ask for something; in order to protect the material system temperature all the time under the state that processing condition require; usually the mobile medium carries out thermal exchange in the interlayer of the serpentine tube of employing inside reactor or reactor outside; finish in the scope of expectation to guarantee temperature of reaction; the most frequently used heat-transfer medium is a water; the heat transfer temperature scope is 10-80 ℃; beyond this temperature range, because water is tending towards freezing or boiling and can not make heat transferring agent and use.The advantage of making heat transferring agent with water is that heat-transfer effect is good, with low cost, but under lower temperature reaction process is carried out thermal exchange, and it is powerless that water just seems.Than the process of cooling of carrying out under the low reaction temperatures than hard intensity, usually the heat exchange secondary refrigerant that adopts has the inorganic salts solution that reduces freezing point for some, as sodium nitrate aqueous solution, aqueous sodium carbonate, sodium chloride aqueous solution, calcium chloride waters etc., this class heat transferring medium is serious to various metals (carbon steel, stainless steel, brass, aluminium and aluminium alloy) surface corrosion.At the protection against corrosion problem of low-temperature heat exchange secondary refrigerant, existing a lot of report, but its Application Areas mainly concentrates on the automobile antifreeze solution aspect, for the report of other industrial circle seldom.As Chinese patent 02126622.0 (a kind of antifreezing liquid resisting corrosion, deposit and boiling for car), 200610015513.5 (automobile engine winterization fluids), 200710020073.7 (automobile antifreeze solutions), 200410021183.1 (railway carriage deicing fluid and compound method thereof), 200410043938.8 (a kind of multi-usage deicing fluid) etc.The major ingredient great majority are selected glycols for use in the automobile antifreeze solution, this class deicing fluid is higher because of boiling point, volatility is little, deicing fluid when being fit to do cooling fluid under the such comparatively high temps of motor car engine and engine stoping operation, but be not suitable for doing the cooling fluid of the recycle system under the lesser temps, when low temperature (as-30 ℃), the viscosity of aqueous glycol solution can increase sharply, and circulation resistance is very big.To the fermentation (beer, soy sauce, edible vinegar etc.) of food aspect and the heat-exchange system secondary refrigerant of bio-pharmaceuticals aspect, should satisfy the requirement of thermal exchange, certain health toxicity requirement is arranged again, it is open to avoid a spot of leakage to cause the secondary refrigerant of great personal injury not see, thereby the present invention has remedied the prior art deficiency.
Summary of the invention
The objective of the invention is to have overcome existing defective in the prior art, a kind of multiple efficacies such as carrying cold, anticorrosion, antirust, antibacterial, algae removal that has is provided, at a lower temperature, be mainly used in the cold heat transfer liquids refrigerant that carries in chemical pharmacy and biological fermentation industrial production field.
The secondary refrigerant of a kind of industrial low-temperature heat exchange of the present invention has the corrosion protection antiscale to various metals (carbon steel, stainless steel, brass, aluminium and aluminium alloy etc.) surface, and its technical scheme of taking is by water, C
1～C
4Organic pure and mild multiple functional additive is formed, and its characteristics are that this low-temperature heat exchange secondary refrigerant forms (by weight percentage) by following component:
Water 5～90%,
C
1～C
4It is organic pure 5～90%,
Functional additive 0.5～2%,
Wherein: dispersion agent 0.01～0.5%,
Inhibiter 0.01～1.5%,
PH value conditioning agent 0.01～1.0%.
The secondary refrigerant of a kind of industrial low-temperature heat exchange of the present invention, selected C
1～C
4Organic alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol, propylene glycol, glycerol and Diethylene Glycol, and according to the use temperature scope, these alcohol can be selected for use separately, also can mix use in varing proportions, in the hope of obtaining best heat-transfer effect.For example, under the temperature condition more than 80 ℃, reactive system is carried out heat exchange, mainly with glycol or ternary alcohols, to reduce the volatilization loss of heat-transfer medium, and in the low temperature environment below 10 ℃, then mainly select the organic alcohol of single alcohols for use, have very low freezing point and good flowability to guarantee the low-temperature heat exchange secondary refrigerant.
The secondary refrigerant of a kind of industrial low-temperature heat exchange of the present invention, consider the cost of raw material and the particular requirement of sanitary condition aspect, selected inhibiter is water glass, Sodium Nitrite, tertiary sodium phosphate, Sodium hexametaphosphate 99, trisodium phosphate, phenylformic acid (sodium), phenylpropyl alcohol triazole.Wherein, phenylformic acid (sodium) also has bacteriostatic action.According to the difference of heat-transfer system material, above inhibiter also can use separately or several mixing is used, and it is 0.01～1.5% of heat-transfer medium gross weight that inhibiter adds total amount.
The secondary refrigerant of a kind of industrial low-temperature heat exchange of the present invention, selected dispersion agent are ethylenediamine tetraacetic acid (EDTA) (EDTA), disodium ethylene diamine tetraacetate (EDTA-Na
2), complexon I (NTA), hydroxyethylethylene diamine tri-acetic acid (HEDTA), Sunmorl N 60S, different according to the difference of heat-transfer system material and trace soluble metal ion, these dispersion agents can use separately or several mixing is used, and it is 0.01～0.5% of heat-transfer medium gross weight that dispersion agent adds total amount.
The secondary refrigerant of a kind of industrial low-temperature heat exchange of the present invention, selected pH value conditioning agent is sodium hydroxide, yellow soda ash, sodium bicarbonate, potassium hydroxide, these pH value conditioning agents can use separately or several mixing is used, adjust pH value in 7～9 scope, it is 0.01～1.0% of heat-transfer medium gross weight that the pH value conditioning agent adds total amount.Because when pH value is lower than 7, some inhibiter is with ineffective, and corrosion phenomenon can take place.
Major advantage of the present invention is: invented and a kind ofly can be applied to multiple Industrial processes, requirement according to heat transfer process, the low-temperature heat exchange secondary refrigerant can be selected the design proportioning raw materials in temperature range between-80 ℃～120 ℃, prepare have corrosion protection, the high efficient cryogenic heat exchange secondary refrigerant of scale inhibition, antibacterial, algae removal effect.
The invention will be further described below by embodiment.
Embodiment
Table 1, table 2, table 3 and table 4 have provided the relation between four kinds of organic alcohol solution concentration and the freezing point respectively, as by the low-temperature heat exchange secondary refrigerant freezing point of mixing organic alcohol preparation, can utilize that each organic alcohol carries out the freezing point that simple arithmetic adds and predict product to the contribution of freezing point in the following table.
Table 1 methanol aqueous solution freezing point
| The methanol aqueous solution freezing point (℃) | Weight content % | The methanol aqueous solution freezing point (℃) | Weight content % |
| ??-53 | ??50 | ??-27 | ??23.5 |
| ??-47 | ??45.5 | ??-25 | ??21.7 |
| The methanol aqueous solution freezing point (℃) | Weight content % | The methanol aqueous solution freezing point (℃) | Weight content % |
| ??-45 | ??42 | ??-23 | ??20 |
| ??-42 | ??38.5 | ??-22 | ??18.5 |
| ??-36 | ??33.3 | ??-20 | ??17.2 |
| ??-33 | ??29.5 | ??-19 | ??16.1 |
| ??-27 | ??26.3 | ??-18 | ??15.15 |
Table 2 aqueous ethanolic solution freezing point
| The aqueous ethanolic solution freezing point (℃) | Weight content % | The aqueous ethanolic solution freezing point (℃) | Weight content % |
| ??-112 | ??100 | ??-44.8 | ??40 |
| ??-100 | ??90 | ??-33.6 | ??30 |
| ??-89.6 | ??80 | ??-22.4 | ??20 |
| ??-78.4 | ??70 | ??-11.2 | ??10 |
| ??-67.2 | ??60 | ??0.0 | ??0.0 |
| ??-56 | ??50 |
Table 3 aqueous glycol solution freezing point
| Aqueous glycol solution freezing point ℃ | Ethylene glycol weight % | Aqueous glycol solution freezing point ℃ | Ethylene glycol weight % |
| ??-10 | ??28.4 | ??-50 | ??59.9 |
| ??-15 | ??32.8 | ??-68 | ??68.1 |
| ??-20 | ??38.5 | ??-60 | ??70.0 |
| ??-25 | ??45.3 | ??-45 | ??82.7 |
| ??-30 | ??47.8 | ??-40 | ??86.1 |
| Aqueous glycol solution freezing point ℃ | Ethylene glycol weight % | Aqueous glycol solution freezing point ℃ | Ethylene glycol weight % |
| ??-35 | ??50.9 | ??-30 | ??93.2 |
| ??-40 | ??54.7 | ??-20 | ??97 |
| ??-45 | ??57.0 | ??-15 | ??100 |
Table 4 aqueous glycerin solution freezing point
| Aqueous glycerin solution freezing point ℃ | Glycerine (weight) % | Aqueous glycerin solution freezing point ℃ | Glycerine (weight) % |
| ??-10 | ??31.9 | ??-30 | ??63.8 |
| ??-15 | ??42.9 | ??-35 | ??69.2 |
| ??-20 | ??51.2 | ??-40 | ??72.8 |
| ??-25 | ??58.3 | ??-45 | ??76.5 |
Embodiment 1:
The low-temperature heat exchange secondary refrigerant that a kind of weight percent is composed as follows:
Ethanol 30%
Ethylene glycol 20%
Tertiary sodium phosphate 0.5%
Sodium Benzoate 0.5%
Water glass 0.2%
Benzotriazole 0.1%
Sodium hydroxide 0.1%
EDTA disodium 0.1%
Sunmorl N 60S 0.2%
Water 48.30%
This low-temperature heat exchange secondary refrigerant freezing point is-40 ℃, can be used in the material cooling system such as beer fermentation, pharmacy under 0～-10 ℃ of environment in the Northeast's winter, iron and steel, brass, aluminium material are not all had the burn into non-scaling, do not go mouldy, and the anti-corrosion performance comparative experiments to test piece of this low-temperature heat exchange secondary refrigerant and tap water, spirituous solution the results are shown in Table 5:
Table 5 different media compares the corrosive nature of test piece
Test conditions is: normal pressure, and indoor natural temperature ℃ adopts iron and steel, brass, the aluminium material test piece of 50 * 25 * 0.3mm to carry out anti-corrosion performance test, assesses the anti-corrosion performance of test solution by periodic measurement test piece accumulative total loss of weight, and according to the corrosion rate formula:
Calculate the corrosion rate of different solutions to various metals.The low-temperature heat exchange secondary refrigerant that can find out embodiment 1 from table 5 only has slight corrosion to steel disc, and corrosion rate is annual every square metre of 0.6g, and tap water and alcohol water are then all very serious to the corrosion of iron and steel, copper, aluminium.
Embodiment 2:
The percentage composition of low-temperature heat exchange secondary refrigerant is as follows:
Ethylene glycol 30%
Diethylene Glycol 10%
Trisodium phosphate 0.3%
Sodium Benzoate 0.2%
Sodium Nitrite 0.2%
Benzotriazole 0.1%
Sodium hydroxide 0.1%
Complexon I (NTA) 0.1%
Water 59.00%
The freezing point of this low-temperature heat exchange secondary refrigerant is below-20 ℃, boiling point is more than 120 ℃, volatility is very little during normal temperature, be used under-10～80 ℃ the temperature condition of complicated biological chemistry pharmacy low-temperature cooling system, in the chemical reaction system that heating and cooling hocket, iron and steel, copper, aluminium are not had the burn into non-scaling, never degenerate.An amount of on the other hand inhibiter that adds also has the effect that suppresses the component volatilization and reduce freezing point.
Embodiment 3:
Low-temperature heat exchange secondary refrigerant weight percent is composed as follows:
Methyl alcohol 41%
Sodium hexametaphosphate 99 0.4%
Sodium Nitrite 0.3%
Sodium bicarbonate 0.2%
Disodium ethylene diamine tetraacetate 0.1%
Water 58.00%
The freezing point of the low-temperature heat exchange secondary refrigerant of present embodiment is below-40 ℃, be used in north of china in winter, utilize outdoor natural low temperature environment, the thermal exchange for preparing the leavening temperature control of acetone, Virahol with fermentation method, this system has cheap, lower use temperature and good low-temperature fluidity.Iron and steel there is not corrosion.
Embodiment 4:
Low-temperature heat exchange secondary refrigerant weight percent is composed as follows:
Ethanol 20%
Sodium hexametaphosphate 99 0.5%
Sodium Benzoate 0.1%
Sunmorl N 60S 1.0%
Benzotriazole 0.05%
Potassium hydroxide 0.05%
Water 78.30%
The freezing point of the low-temperature heat exchange secondary refrigerant of present embodiment is used in-10 ℃～40 ℃ temperature range below-20 ℃.Be used in the place that refrigerant is had strict toxicity requirement, this system has cheap, lower use temperature and good low-temperature fluidity, even a spot of leakage is arranged, also can not cause bigger potential safety hazard to product, and metallic substance is not had corrosion.
The above record only for utilizing the embodiment of the technology of the present invention content, anyly is familiar with modification that this operator uses the present invention to do, variation, all belonged to the claim that the present invention advocates, and be not limited to cited embodiment.
Claims (6)
1. the secondary refrigerant of an industrial low-temperature heat exchange is by water, C
1～C
4Organic pure and mild multiple functional additive is formed, and it is characterized in that by water 5～90%, C
1～C
4Organic pure 5～90%, functional additive 0.5～2% component is formed.
2. the secondary refrigerant of a kind of industrial low-temperature heat exchange according to claim 1 is characterized in that described C
1～C
4Organic alcohol is selected one or more mixing in them of methyl alcohol, ethanol, ethylene glycol, Diethylene Glycol, propylene glycol, glycerol for use.
3. the secondary refrigerant of a kind of industrial low-temperature heat exchange according to claim 1 is characterized in that described functional additive is made up of dispersion agent 0.01～0.5%, inhibiter 0.01～1.5%, pH value conditioning agent 0.01～1.0%.
4. the secondary refrigerant of a kind of industrial low-temperature heat exchange according to claim 3 is characterized in that described dispersion agent selects ethylenediamine tetraacetic acid (EDTA) (EDTA), disodium ethylene diamine tetraacetate (EDTA-Na for use
2) in them one or more of complexon I (NTA), hydroxyethylethylene diamine tri-acetic acid (HEDTA), Sunmorl N 60S use with, adding total amount is 0.01～0.5% of heat transfer refrigerant gross weight.
5. the secondary refrigerant of a kind of industrial low-temperature heat exchange according to claim 3, it is characterized in that described inhibiter selects for use in them one or more of water glass, Sodium Nitrite, tertiary sodium phosphate, Sodium hexametaphosphate 99, trisodium phosphate, phenylformic acid, phenylpropyl alcohol triazole to use with, adding total amount is 0.01～1.5% of heat transfer refrigerant gross weight.
6. the secondary refrigerant of a kind of industrial low-temperature heat exchange according to claim 3, it is characterized in that described pH value conditioning agent selects for use in them one or more of sodium hydroxide, yellow soda ash, sodium bicarbonate, ammoniacal liquor to use with, pH value is adjusted in 7～9 the scope, and adding total amount is 0.01～1.0% of heat transfer refrigerant gross weight.
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|---|---|---|---|
| CN200910193902A CN101717619A (en) | 2009-11-13 | 2009-11-13 | Industrial low-temperature heat exchange secondary refrigerant |
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|---|---|---|---|
| CN200910193902A CN101717619A (en) | 2009-11-13 | 2009-11-13 | Industrial low-temperature heat exchange secondary refrigerant |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102954647A (en) * | 2012-12-13 | 2013-03-06 | 烟台泰和新材料股份有限公司 | Ethylene glycol coolant circulating system |
| CN103556142A (en) * | 2011-07-27 | 2014-02-05 | 中国科学院宁波材料技术与工程研究所 | Passivation liquid for environment-friendly copper and copper alloy surface and passivation method |
| CN104293310A (en) * | 2013-07-20 | 2015-01-21 | 辽宁润迪精细化工有限公司 | Engine cooling liquid |
| CN104388057A (en) * | 2014-09-18 | 2015-03-04 | 刘胜明 | Low-cost anti-corrosion secondary refrigerant and preparation method thereof |
| CN105088249A (en) * | 2014-05-22 | 2015-11-25 | 上海蓝浦清洗技术有限公司 | Corrosion inhibitor used in refrigerating fluid |
| CN105820801A (en) * | 2016-05-19 | 2016-08-03 | 山东普希环保科技有限公司 | Environment-friendly and economical propylene glycol freezing prevention and boiling prevention fluid |
| CN105969320A (en) * | 2016-07-01 | 2016-09-28 | 南京久鼎制冷空调设备有限公司 | Low-temperature secondary refrigerant containing organic acid salts and application of low-temperature secondary refrigerant |
| CN106244113A (en) * | 2016-08-05 | 2016-12-21 | 江苏河海新能源股份有限公司 | A kind of Environmentally-friendly heat pump working medium and preparation method thereof |
| CN111718693A (en) * | 2020-07-01 | 2020-09-29 | 秦丹志 | Energy conversion liquid |
-
2009
- 2009-11-13 CN CN200910193902A patent/CN101717619A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556142A (en) * | 2011-07-27 | 2014-02-05 | 中国科学院宁波材料技术与工程研究所 | Passivation liquid for environment-friendly copper and copper alloy surface and passivation method |
| CN102954647A (en) * | 2012-12-13 | 2013-03-06 | 烟台泰和新材料股份有限公司 | Ethylene glycol coolant circulating system |
| CN102954647B (en) * | 2012-12-13 | 2015-10-28 | 烟台泰和新材料股份有限公司 | The ethylene glycol coolant circulatory system |
| CN104293310A (en) * | 2013-07-20 | 2015-01-21 | 辽宁润迪精细化工有限公司 | Engine cooling liquid |
| CN105088249A (en) * | 2014-05-22 | 2015-11-25 | 上海蓝浦清洗技术有限公司 | Corrosion inhibitor used in refrigerating fluid |
| CN104388057A (en) * | 2014-09-18 | 2015-03-04 | 刘胜明 | Low-cost anti-corrosion secondary refrigerant and preparation method thereof |
| CN105820801A (en) * | 2016-05-19 | 2016-08-03 | 山东普希环保科技有限公司 | Environment-friendly and economical propylene glycol freezing prevention and boiling prevention fluid |
| CN105969320A (en) * | 2016-07-01 | 2016-09-28 | 南京久鼎制冷空调设备有限公司 | Low-temperature secondary refrigerant containing organic acid salts and application of low-temperature secondary refrigerant |
| CN106244113A (en) * | 2016-08-05 | 2016-12-21 | 江苏河海新能源股份有限公司 | A kind of Environmentally-friendly heat pump working medium and preparation method thereof |
| CN111718693A (en) * | 2020-07-01 | 2020-09-29 | 秦丹志 | Energy conversion liquid |
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Open date: 20100602 |