CN102719224A - Chemical absorption refrigeration working pair - Google Patents
Chemical absorption refrigeration working pair Download PDFInfo
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- CN102719224A CN102719224A CN2011100796489A CN201110079648A CN102719224A CN 102719224 A CN102719224 A CN 102719224A CN 2011100796489 A CN2011100796489 A CN 2011100796489A CN 201110079648 A CN201110079648 A CN 201110079648A CN 102719224 A CN102719224 A CN 102719224A
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- refrigeration working
- working medium
- absorption
- refrigeration
- chemical absorption
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Abstract
The invention discloses a chemical absorption refrigeration working pair, comprising liquid ammonia as a refrigerant and an ionic liquid containing zinc chloride, that is, dizinc pentachloride-1-methyl-3-alkyl imidazole([CnMIm]Zn2Cl5) as an absorbent. Because the absorbent always remains liquid under working conditions and is non-volatile after being heated, the advantages of traditional metal chloride-ammonia refrigeration working pair are kept, and the problems of difficulty in heat and mass transfer of the adsorption bed and easiness in agglomeration and expansion, etc. existing in calcium chloride-ammonia and other solid metal chloride adsorption refrigerating machines in the prior art are solved. The invention can be used in industrial production of refrigeration machinery or heat pumps.
Description
Technical field
It is right to the present invention relates to a kind of chemical absorption formula refrigeration working medium.
Background technology
Thermochemistry adsorption type (or absorption) refrigerator is the energy-conserving and environment-protective technology that can effectively utilize low grade heat energy; It can obtain the required refrigerating duty of people through consuming low grade heat energy; Also can be used as heat pump and use, obtain more but the heat energy that grade is relatively low of quantity through consuming the higher relatively heat energy of a small amount of grade.
Existing thermochemistry adsorbent refrigerator is with metal chloride (MCl
nTo be the right solid-state adsorbent refrigerator of working medium be typical case to)-ammonia, and wherein the most representative is CaCl
2-NH
3System.Yet the fatal shortcoming that this type solid state chemistry absorption type refrigerating working medium is right mainly contains 2 points:
1) heat transfer property extreme difference.MCl
nThermal conductivity very low (for example, the thermal conductivity of calcium chloride is merely 0.1～0.3Wm
-1K
-1) and its particle packing and adsorption bed wall just point contact, cause the heat-transfer capability of whole adsorption bed very poor.
2) be prone to expand and lump.Can occur after multiple adsorb and the desorb expanding and caking phenomenon, make gas transfer worsen, the adsorption and desorption ability descends gradually, even loses efficacy.
Many researchers is done a lot of work from the angle of strengthening the adsorption bed heat and mass.Have at CaCl
2Added a certain proportion of CaSO in the sorbent material
4, the employing sticker that has is with CaCl
2Be bonded to grit, employing metallic particles, gac or silica gel that also has and calcium chloride are formed compound adsorbent and are controlled muriatic expansion and caking, and improve heat transfer property.Yet above-mentioned the whole bag of tricks is not fundamentally broken through the bottleneck problem of muriate adsorption bed heat and mass difficulty.
If the metal chloride sorbent material remains liquid state in the adsorption/desorption process, situation will be made a world of difference, and heat and moisture transfer problems and expansion agglomeration problems all can be readily solved.
Summary of the invention
The object of the present invention is to provide a kind of liquid chemical absorption type heat pump work substance right, to solve the problems such as difficult, the easy expansion of luming of adsorption bed heat and mass that solid metal muriate adsorbent refrigerators such as calcium chloride-ammonia exist.
For realizing above-mentioned purpose, chemical absorption formula refrigeration working medium provided by the invention is right, makes refrigeration agent with liquefied ammonia, contains MCl
nThe imidazole type ion liquid of composition is made chemical absorber and is formed.
Wherein, the imidazole type ion liquid of containing metal muriate composition is pentachloro-ization two zinc-1-methyl-3-alkyl imidazole, and expression formula is [C
nMIm] Zn
2Cl
5, n=2-8.
Compare with aqueous electrolyte liquid with conventional organic solvents, outstanding advantage of the present invention is:
A. liquid wide ranges is from being lower than or near more than the room temperature to 300 ℃, high thermostability and chemicalstability being arranged;
B. vp is very little, and is non-volatile, and mixing with volatile solutes is easy to realize separating and purifying;
C. do not fire not quick-friedly, do not have corrosion, low toxicity is eco-friendly green solvent.
Embodiment
Chemical absorption formula refrigeration working medium provided by the invention is right, is by NH
3With contain MCl
nThe imidazole type ion liquid of composition combines, specifically NH
3With [C
nMIm] Zn
2Cl
5The chemical absorption formula heat pump fluid that (pentachloro-ization two zinc-1-methyl-3-alkyl imidazole) are formed is right.
[C
nMIm] Zn
2Cl
5Be to the muriatic ionic liquid of all stable containing metal of water and air Wei Ying, Zhang Qingguo. zinc-base ionic liquid BMIZn
2Cl
5Property research. chemical journal .2008,66 (16): 1879-1883}.Ionic liquid described here is to refer in particular to the material that is made up of ion that under near temperature room temperature or the room temperature, is in a liquid state.
ZnCl
2-NH
3Also be that a pair of common chemical absorption type refrigerating working medium is right, because 1 mole of Zn
2+At most can with 6 moles NH
3Complex reaction takes place.Zn
2+The aqueous solution also can with NH
3Complex reaction takes place, also like this certainly in ionic liquid.Different is, if adopt the aqueous solution to make the ammonia absorption agent, when solution is regenerated, has both contained ammonia in the gas phase, also contains water vapor, and the two separation needs rectifier unit, system and NH
3-H
2The O absorption system does not have too big difference.Contain Zn and adopt
2+Ionic liquid do the chemical absorber of ammonia, gas phase almost only contains ammonia, absorption agent is easy to realize separating through the input heat with refrigeration agent.
The absorption agent of refrigeration working medium centering according to the invention is in working order down for liquid.Ion liquid thermal conductivity and water are in the same order of magnitude, are good heat-conducting mediums.And main heat exchange form is a liquid liquid convective heat exchange in the absorption/desorption process, and heat transfer property is than traditional solid metal chloride absorption height of bed several magnitude.
In addition, the saturation vapour pressure of ionic liquid under working temperature can be ignored, thereby can realize separating of refrigeration agent and absorption agent easily.
Said absorption agent had both comprised to the sorption of refrigeration agent that physical action (dissolving) also comprised chemisorption, and the latter is main, because the Zn in the absorption agent
2+Ion can generate [Zn (NH with ammonia react
3)
6]
2+, therefore, absorption type refrigeration working medium according to the invention pair and usually said this type of lithium-bromide solution-water working medium are to different.
Through specific embodiment the present invention is described further below, still scope of the present invention has more than and is limited to the scope that embodiment covers.
Chemical absorption formula refrigeration working medium of the present invention is right, can in practical application, constitute single-effective absorption refrigeration cycle or double effect absorption refrigeration cycle with reference to the right form of lithium-bromide solution-water absorption type refrigeration working medium.With the single-effective absorption refrigeration cycle is example, and its mechanical system comprises 4 primary clusterings such as vaporizer, resorber, producer and condensing surface, and the right workflow of refrigeration working medium is following:
One, refrigeration agent evaporation is carried out in vaporizer, and process need takes place being higher than under the condition of vaporization temperature, absorbs heat from environment, thereby produces refrigeration.Right specific to working medium according to the invention, establishing vaporization temperature is 0 ℃, and the saturation vapour pressure of corresponding liquefied ammonia is 430kPa, can export about 5 ℃ cold water to environment.
Two, refrigerant vapour absorbs, and in resorber, carries out.Because resorber is communicated with the gas phase of vaporizer, so this process and refrigeration agent evaporation take place synchronously.In the process; Need not be higher than absorption temperature to keep the absorbent solution temperature to the environment heat release; At absorption agent before reaction does not reach the chemical equilibrium point under the absorption temperature for the chemical absorption of refrigeration agent; The sustainable generation of process, the interior gas phase vapour pressure of resorber this moment is lower than the gas phase vapour pressure in the vaporizer.Right specific to working medium according to the invention, absorption temperature can be up to 110 ℃, and corresponding chemical absorption molecular balance pressure is about 400kPa, during molecular balance, and every mole of Zn
2+Can absorb 4 moles of NH
3([Zn (NH
3)
2]
2+→ [Zn (NH
3)
6]
2+).Simultaneously, absorption process can be exported 70～100 ℃ hot water or the steam of 0.1MPa to environment.
Three, absorbent regeneration carries out in producer.With in the resorber near the absorption agent of saturated absorption state through pump delivery to revivifier; The heat that is higher than regeneration temperature from the environment input; Destroy the chemical reaction equilibrium between absorption agent and the refrigeration agent; Refrigeration agent is evaporated, makes absorption agent be returned to original state, then it is sent back to resorber.Right specific to working medium according to the invention, occurrence temperature need be higher than 140 ℃, and corresponding ammonia vapour pressure is 1300kPa, means heat source temperature from the environment input greatly about more than 150 ℃, and the chemical transformation that this moment, absorption agent took place is [Zn (NH
3)
6]
2+→ [Zn (NH
3)
2]
2+, import more high-grade thermal source, reaction can be proceeded all to remove until complexing ammonia.
Four, high-pressure refrigerant vapor condensation is carried out in condensing surface.Evaporate the refrigerant vapour that in the producer, flow into condensing surface, under condensing temperature, be condensed into liquid state, get back to vaporizer through throttling set then, thereby constitute refrigeration cycle through pipeline.Condensing temperature is generally envrionment temperature, and condensation process need be dispelled the heat to environment.Right specific to working medium according to the invention, condensing temperature is made as 30 ℃, and corresponding ammonia saturation vapour pressure is 1166kPa, is lower than ammonia pressure in the producer, thereby condensation can take place.
Said process is the single-effective absorption refrigeration cycle; Utilize refrigeration working medium according to the invention right; Can also constitute double effect absorption refrigeration cycle, multiple-effect Absorption Cooling System and absorption heat pump circulation, also can circulate to constituting compound-refrigerating with other absorption type refrigeration working mediums.
Claims (4)
1. a chemical absorption formula refrigeration working medium is right, is to be refrigeration agent with liquefied ammonia, and the imidazole type ion liquid of containing metal muriate composition is that chemical absorber is formed, and wherein ion liquid positively charged ion is made up of the Methylimidazole positively charged ion that contains alkyl substituent.
2. chemical absorption formula refrigeration working medium according to claim 1 is right, and wherein, alkyl substituent is one or more different alkyl substituents.
3. right according to the said chemical absorption formula of claim 1 refrigeration working medium, wherein, the imidazole type ion liquid of containing metal muriate composition is pentachloro-ization two zinc-1-methyl-3-alkyl imidazole, and expression formula is [C
nMIm] Zn
2Cl
5, n=2-8.
4. right according to the said chemical absorption formula of claim 1 refrigeration working medium, wherein, the substituting group of positively charged ion dialkylimidazolium ion 1 position is straight chain or the substituting group that has side chain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110079648.9A CN102719224B (en) | 2011-03-31 | 2011-03-31 | Chemical absorption refrigeration working pair |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110079648.9A CN102719224B (en) | 2011-03-31 | 2011-03-31 | Chemical absorption refrigeration working pair |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102719224A true CN102719224A (en) | 2012-10-10 |
| CN102719224B CN102719224B (en) | 2015-01-07 |
Family
ID=46945102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110079648.9A Expired - Fee Related CN102719224B (en) | 2011-03-31 | 2011-03-31 | Chemical absorption refrigeration working pair |
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| Country | Link |
|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1957057A (en) * | 2004-05-21 | 2007-05-02 | 巴斯福股份公司 | Novel pairs of working substances for absorption heat pumps, absorption refrigeration machines and heat transformers |
-
2011
- 2011-03-31 CN CN201110079648.9A patent/CN102719224B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1957057A (en) * | 2004-05-21 | 2007-05-02 | 巴斯福股份公司 | Novel pairs of working substances for absorption heat pumps, absorption refrigeration machines and heat transformers |
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| Publication number | Publication date |
|---|---|
| CN102719224B (en) | 2015-01-07 |
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| C14 | Grant of patent or utility model | ||
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Granted publication date: 20150107 Termination date: 20210331 |