CN102719224B - Chemical absorption refrigeration working pair - Google Patents
Chemical absorption refrigeration working pair Download PDFInfo
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- CN102719224B CN102719224B CN201110079648.9A CN201110079648A CN102719224B CN 102719224 B CN102719224 B CN 102719224B CN 201110079648 A CN201110079648 A CN 201110079648A CN 102719224 B CN102719224 B CN 102719224B
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- China
- Prior art keywords
- absorption
- ammonia
- refrigeration
- heat
- refrigeration working
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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
The present invention relates to a kind of chemical absorption formula refrigeration working medium pair.
Background technology
Thermochemistry adsorption type (or absorption) refrigerator is an energy-conserving and environment-protective technology that effectively can utilize low grade heat energy, it can by consuming the refrigerating duty of low grade heat energy acquisition needed for people, also can using as heat pump, obtaining the more but heat energy that grade is relatively low of quantity by consuming the relatively high heat energy of a small amount of grade.
Existing thermochemistry adsorbent refrigerator, with metal chloride (MCl
n)-ammonia is working medium, and right solid adsorbant formula refrigerator is the most typical, and wherein most is representational is CaCl
2-NH
3system.But the fatal defects that this kind of 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 (such as, the thermal conductivity of calcium chloride is only 0.1 ~ 0.3Wm
-1k
-1) and its particle packing and adsorption bed wall be point cantact, cause the heat-transfer capability of whole adsorption bed very poor.
2) easily expand and lump.There will be expansion and caking phenomenon after multiple adsorb and desorb, gas transfer is worsened, and adsorption and desorption ability declines gradually, even loses efficacy.
Many researchers is done a lot of work from the angle of strengthening adsorption bed heat and mass.Have at CaCl
2a certain proportion of CaSO is added in sorbent material
4, some employing binding agents are by CaCl
2be bonded to grit, the employing metallic particles, gac or the silica gel that also have and calcium chloride form compound adsorbent to control muriatic expansion and caking, and improve heat transfer property.But above-mentioned various method does not fundamentally break through the bottleneck problem of muriate adsorption bed heat and mass difficulty.
If metal chloride sorbent material remains liquid in 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 pair, to solve the problem such as adsorption bed heat and mass difficulty, the expansion of easy caking that the solid metal chloride adsorbent refrigerators such as Fullerenes chloride exist.
For achieving the above object, chemical absorption formula refrigeration working medium pair provided by the invention, makes refrigeration agent with liquefied ammonia, containing MCl
nthe imidazole type ion liquid of composition is made chemical absorber and forms.
Wherein, the imidazole type ion liquid of containing metal muriate composition is phosphoric two zinc-1-methyl-3-alkyl imidazoles, and expression formula is [C
nmIm] Zn
2cl
5, n=2-8.
Compare with aqueous electrolyte liquid with conventional organic solvents, outstanding advantages of the present invention is:
A. liquid state range is wide, from lower than or close to room temperature to more than 300 DEG C, have high thermostability and chemical stability;
B. vapour pressure is very little, non-volatile, and mixing with volatile solutes is easy to realize abstraction and purification;
C. not firing not quick-fried, corrosion-free, low toxicity, is eco-friendly green solvent.
Embodiment
Chemical absorption formula refrigeration working medium pair provided by the invention is by NH
3with containing MCl
nthe imidazole type ion liquid of composition combines, NH specifically
3with [C
nmIm] Zn
2cl
5the chemical absorption formula heat pump fluid pair that (phosphoric two zinc-1-methyl-3-alkyl imidazoles) form.
[C
nmIm] Zn
2cl
5be to the containing metal that water and air is all stable muriatic ionic liquid Wei Ying, Zhang Qingguo. zinc-base ionic liquid BMIZn
2cl
5character research. chemical journal .2008,66 (16): 1879-1883}.Ionic liquid described here refers in particular to the material be made up of ion be in a liquid state under room temperature or near room temperature temperature.
ZnCl
2-NH
3also be the chemical adsorption refrigeration working medium pair commonly used for a pair, because 1 mole of Zn
2+at most can with the NH of 6 moles
3there is complex reaction.Zn
2+the aqueous solution also can with NH
3there is complex reaction, certainly also like this in ionic liquid.Unlike, if adopt the aqueous solution to make ammonia absorption agent, when regeneration of waste liquor, both containing ammonia in gas phase, also containing water vapor, the two separation needs rectifier unit, system and NH
3-H
2o absorption system does not have too large difference.And adopt containing Zn
2+ionic liquid do the chemical absorber of ammonia, gas phase is almost only containing ammonia, and absorption agent realizes being separated easily via inputting heat with refrigeration agent.
The absorption agent of refrigeration working medium centering of the present invention is lower to liquid in working order.The thermal conductivity of ionic liquid and water are in the same order of magnitude, are good heat-conducting mediums.And heat exchange form main in absorption/desorption process is liquid liquid convective heat exchange, the heat transfer property order of magnitude more several than traditional solid metal chloride absorption height of bed.
In addition, ionic liquid saturation vapour pressure is at the working temperature negligible, thus can realize being separated of refrigeration agent and absorption agent easily.
Described absorption agent had both comprised physical action (dissolving) to the sorption of refrigeration agent and had also comprised chemisorption, and the latter is main, because the Zn in absorption agent
2+ion can generate [Zn (NH with ammonia react
3)
6]
2+, therefore, absorption type refrigeration working medium of the present invention pair with usually said this kind of working medium of lithium-bromide solution-water to different.
Below by specific embodiment, the invention will be further described, but scope of the present invention has more than the scope being limited to embodiment and covering.
Chemical absorption formula refrigeration working medium pair of the present invention, can form single-effective absorption refrigeration cycle or double effect absorption refrigeration cycle in actual applications with reference to the form that lithium-bromide solution-water absorption type refrigeration working medium is right.For single-effective absorption refrigeration cycle, its mechanical system comprises 4 primary clusterings such as vaporizer, resorber, producer and condenser, and the right workflow of refrigeration working medium is as follows:
One, refrigeration agent evaporation, carry out in vaporizer, process need occurs under higher than the condition of vaporization temperature, absorbs heat from environment, thus produces refrigeration.Specific to working medium pair of the present invention, if vaporization temperature is 0 DEG C, the saturation vapour pressure of corresponding liquefied ammonia is 430kPa, can export the cold water of about 5 DEG C to environment.
Two, refrigerant vapour absorbs, and carries out in resorber.Because resorber is communicated with the gas phase of vaporizer, so this process and refrigeration agent evaporate synchronous generation.In process, need to environment heat release to maintain absorbent solution temperature not higher than absorption temperature, before absorption agent does not reach the chemical equilibrium point under absorption temperature for the chemical absorption reaction of refrigeration agent, the sustainable generation of process, the gas phase vapour pressure now in resorber is lower than the gas phase vapour pressure in vaporizer.Specific to working medium pair of the present invention, absorption temperature can up to 110 DEG C, and corresponding chemical absorption molecular balance pressure is about 400kPa, during molecular balance, and every mole of Zn
2+absorbable rod 4 moles of NH
3([Zn (NH
3)
2]
2+→ [Zn (NH
3)
6]
2+).Meanwhile, absorption process can export the hot water of 70 ~ 100 DEG C or the steam of 0.1MPa to environment.
Three, absorbent regeneration, carries out in producer.By in resorber close to the absorption agent of saturated absorption state by pump delivery to revivifier, the heat higher than regeneration temperature is inputted from environment, destroy the chemical reaction equilibrium between absorption agent and refrigeration agent, refrigeration agent is evaporated, make absorption agent be returned to original state, then sent back to resorber.Specific to working medium pair of the present invention, occurrence temperature need higher than 140 DEG C, and corresponding ammonia vapour pressure is 1300kPa, and mean that the heat source temperature inputted from environment is greatly about more than 150 DEG C, the chemical transformation that now absorption agent occurs is [Zn (NH
3)
6]
2+→ [Zn (NH
3)
2]
2+, input more high-grade thermal source, reaction can proceed until complexing ammonia all removes.
Four, high-pressure refrigerant vapor condensation, carries out in condenser.The refrigerant vapour evaporated in producer, flows into condenser by pipeline, is condensed into liquid state, then gets back to vaporizer by throttling set under condensing temperature, thus forms refrigeration cycle.Condensing temperature is generally envrionment temperature, and condensation process needs to function of environment heat emission.Specific to working medium pair of the present invention, condensing temperature is set to 30 DEG C, and corresponding ammonia saturation vapour pressure is 1166kPa, lower than ammonia pressure in producer, thus condensation can occur.
Said process is single-effective absorption refrigeration cycle, utilize refrigeration working medium pair of the present invention, double effect absorption refrigeration cycle, multiple-effect absorption refrigeration cycle and absorption heat pump cycle can also being formed, also can circulate to forming compound-refrigerating with other absorption type refrigeration working mediums.
Claims (1)
1. a chemical absorption formula refrigeration working medium pair, is take liquefied ammonia as refrigeration agent, and the imidazole type ion liquid of containing metal muriate composition is chemical absorber composition, and wherein the positively charged ion of ionic liquid is phosphoric two zinc-1-methyl-3-alkyl imidazoles, and expression formula is [C
nmIm] Zn
2cl
5, n=2-8.
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 CN102719224A (en) | 2012-10-10 |
| CN102719224B true 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102719224B (en) |
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 |
|---|---|
| CN102719224A (en) | 2012-10-10 |
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Granted publication date: 20150107 Termination date: 20210331 |
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| CF01 | Termination of patent right due to non-payment of annual fee |