CN1151906A - Zeolite refrigerating absorbent capable of replacing freon - Google Patents
Zeolite refrigerating absorbent capable of replacing freon Download PDFInfo
- Publication number
- CN1151906A CN1151906A CN 95113984 CN95113984A CN1151906A CN 1151906 A CN1151906 A CN 1151906A CN 95113984 CN95113984 CN 95113984 CN 95113984 A CN95113984 A CN 95113984A CN 1151906 A CN1151906 A CN 1151906A
- Authority
- CN
- China
- Prior art keywords
- refrigerating
- ion
- zeolite
- absorbent
- adsorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000010457 zeolite Substances 0.000 title claims abstract description 23
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 20
- 230000002745 absorbent Effects 0.000 title claims description 18
- 239000002250 absorbent Substances 0.000 title claims description 18
- 239000003463 adsorbent Substances 0.000 claims abstract description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 12
- 239000012013 faujasite Substances 0.000 claims abstract description 12
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 239000004927 clay Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims 3
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000001110 calcium chloride Substances 0.000 claims 1
- 229910001628 calcium chloride Inorganic materials 0.000 claims 1
- 159000000007 calcium salts Chemical class 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000005057 refrigeration Methods 0.000 abstract description 14
- 229910001868 water Inorganic materials 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000465 moulding Methods 0.000 abstract description 5
- 238000003795 desorption Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000000320 mechanical mixture Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229940059936 lithium bromide Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
- F25B17/08—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt
Landscapes
- Sorption Type Refrigeration Machines (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The zeolite refrigeration adsorbent is Ca ion modified Na-faujasite with SiO2/Al2O3 ratio of 2.5-5.5. The said adsorbent has extremely high hydroscopicity and fast water-adsorption and desorption speed under low water vapour pressure. It has refrigeration amount as high as 490-540 KJ/Kg in one water-adsorption and desorption circulation between 20 and 200 deg.C. It is prepared by ion exchange process with Na-faujasite as carrier of Ca ions and moulding while adding clay. It is used as refrigerating adsorbent in refrigerator and air conditioner with water as working medium pair.
Description
The present invention relates to a kind of Zeolite refrigerating absorbent and the preparation method.Specifically preparing a kind of being suitable for for what do refrigeration or idle call is the Zeolite refrigerating absorbent of big, the COP stable performance of needed refrigerating capacity in the right refrigeration machine of working medium with water.
Along with the raising of development and national economy and living standards of the people, the use of Refrigeration ﹠ Air-Conditioning equipment also grows with each passing day, and refrigeration also grows with each passing day with the use of outage equipment, is widely used in refrigeration, the chlorofluoromethane refrigerant (R of control accent equipment
11, R
12) generally acknowledged that atmospheric ozone layer is had destruction, make the greenhouse effects aggravation, directly threaten the ecological balance in the whole world and human healthy. oneself is decided by to ban use of in 1996 in the world.Thereby the substitute of actively developing chlorofluoromethane refrigerant just becomes a very urgent important topic.
Exploitation at present both at home and abroad has two kinds with the equipment without the freon refrigeration machine of research: i.e. lithium-bromide absorption-type refrigerating machine and solid adsorption refrigeration machine.The two is compared, and the latter has that the adsorbent cost is low, and refrigerating capacity is big, the COP height, and the RAM superior performance does not have that corrosion is pollution-free, and one time cost of investment is low, and operating cost is low, and operating maintenance is convenient and be not afraid of vibration and series of advantages such as rock.Still be a kind of new technology at present in the world.Its relevant refrigerating absorbent does not have report as yet.
Purpose of the present invention provides the Zeolite refrigerating absorbent in a kind of alternative fluorine Lyons.
Zeolite refrigerating absorbent of the present invention is characterized in that containing with employing the SiO of Ca ion
2/ Al
2O
3It is 2.5～5.5 Na-faujasite.The weight ratio of each constituent content is in this adsorbent: Ca ion (in CaO): 0.1～10%; The Na ion is (with Na
2The O meter): 2.5～11%; Zeolite: 75～90%; All the other are the alumino-silicate adhesive.The material that can be used as adhesive is a clay, diatomite etc.
The adsorbent of the invention described above at room temperature adsorbs and can if adopt two refrigerating absorbent pillar alternate cycles operations, then can continuously produce cold up to 540 (the dried zeolites of kilojoule/kilogram) in its refrigerating capacity of cycling of 200 ℃ of left and right sides desorptions.Another advantage of adsorbent of the present invention is to have high water absorption under very low water partial pressure, and (example is at 20 ℃ of following P
H2O=
This illustrates that it can make in the system dividing potential drop of water maintain under the state that is bordering on vacuum rapid evaporation and absorbs a large amount of gas latent heat, reaches high refrigeration.Refrigerating absorbent has rate of water absorption and the fast advantage of rate of water loss, so can shorten the operation cycle in the adsorption/desorption balance cycling of refrigeration machine, improves the refrigerating efficiency of unit interval.This refrigerating absorbent fully can substituted freon as a kind of highly effective refrigeration agent.
The preparation method of Zeolite refrigerating absorbent of the present invention is characterized in that exchanging with the Ca ion with commodity or synthetic Na-faujasite, and making Ca ion concentration (in the weight of CaO) is 0.1～10% of adsorbent.Preparation method's (synthetic zeolite) is the NaOH of the concentration known that will be prepared particularly, sodium metaaluminate (NaOH+Al (OH)
3) and waterglass by following gram molecule ratio range:
SiO/Al
2O
3=3～20, Na
2O/SiO
2=0.5～1.5, H
2O/Na
2O-35～90 make a kind of uniform unbodied alumino-silicate gel.After treating into glue, this reaction mixture gel was at room temperature worn out 2～24 hours, place the stainless steel synthesis reactor to be warmed up to 100 ℃ then and carry out crystal about 15～30 hours, can synthesize SiO
2/ Al
2O
3Than the faujasite product between 2.5～5.5.Also can adopt the method that adds crystallization director so as to shortening crystallization time, improve degree of crystallinity.The ratio range of its crystallization director is (4～16) Na
2O.Al
2O
3. (3.5～15) SiO
2. (180～320) H
2O is by the uniform reaction mixture gel of this ratio range preparation under room temperature aging 5 hours, in the above-mentioned reaction mixture gel of preparing of ratio adding by 5% (volume), 100 ℃ of following crystallization 10～18 hours, can make degree of crystallinity than higher and SiO
2/ Al
2O
3The Na-faujasite product of ratio between 2.5～5.5.Exchange with Ca ion and zeolite then, making Ca ion concentration (in the weight of CaO) is 0.1～10% of adsorbent.Concrete preparation is to get a certain amount of Na-faujasite zeolite by Na
+/ Ca
++Adding an amount of concentration than the charge ratio between 2.2～1.8 is the CaCl of 0.2～1.0M
2Solution carries out ion-exchange 2～4 hours between 80～100 ℃.Again after filtration, after washing, drying and the roasting, add clay, after mechanical mixture evenly reaches moulding (spin or extrusion) respectively 3～120 ℃ dry 2～10 hours and made in 2～8 hours down 500～800 ℃ of roastings.Give further instruction below by embodiment to technology of the present invention.
Embodiment 1
With raw materials such as waterglass, sodium aluminate, NaOH and water according to 5Na
2O.Al
2O
3.200H
2The charge ratio of O is made a kind of uniform reaction mixture gel, at room temperature aging 5 hours, place then and be warmed up to 100 ℃ of left and right sides crystallization 24 hours in the stainless steel synthesis reactor, after filtration, can obtain a kind of faujasite product of sodium ion shape after washing and the oven dry, this product is pressed Na
+/ Ca
++Than the charge ratio that is about 2.2, adding an amount of concentration is 0.5MCal
2Solution is 95 ℃ of following ion-exchanges 2 hours, wash after filtration and divide in addition 100 ℃ with 550 ℃ of dry down and roastings 2 hours, its CaO content is 7.0% (weight).Take by weighing clay and a spot of sodium carboxymethylcellulose of a certain amount of product fusion 18% (weight), after mechanical mixing, moulding, drying and roasting, get product.Prepared product descends the dehydration refrigerating capacitys that balancing run obtained up to 540 (kilojoules/kilogram zeolite) 200 ℃ of 20 ℃ of following suctions.
Embodiment 2
By the reaction mixture gel of above-mentioned example 1 preparation, add the crystallization director of 5% (volume), stirring is placed on the stainless steel synthesis reactor and is warmed up to 100 ℃ of crystallization 15 hours, can synthesize the Na-faujasite.Take by weighing a certain amount of this product and add an amount of Na
+/ Ca
++=1.8, concentration is the CaCl of 0.3M
2Solution carries out ion-exchange 2 hours under 85 ℃, promptly get the adsorbent product, its CaO content 5% (weight).Take by weighing clay and a spot of sesbania powder of a certain amount of this adsorbent product fusion 20% (weight) again, prepared adsorbent after mechanical agitation evenly reaches moulding, 20 ℃ of suctions down, 200 ℃ of prepared refrigerating capacitys of balancing run of dewatering down are 530 (the dried zeolites of kilojoule/kilogram).
Example 3
With raw materials such as waterglass, sodium aluminate, NaOH and water with 4Na
2OAl
2O
38SiO
2320H
2The charge ratio of O is made a kind of uniform reaction mixture gel, adds the above-mentioned crystallization director of 5% (volume), evenly is placed in the stainless steel synthesis reactor through mechanical mixture and about 15 hours, then makes out a kind of SiO in 100 ℃ of following crystallization
2/ Al
2O
3The product of=4.1 Na-faujasite.Again by the method CaCl of example 1 and 2
2Solution carried out ion-exchange 2 hours, and after Lu, washing, drying and roasting, it is 3.1% (weight) that the product of gained contains CaO.Get a certain amount of this product and add that prepared adsorbent is 490 (the dried zeolites of kilojoule/kilogram) in 20 ℃ of suctions, 200 ℃ of dehydration refrigerating capacitys that balancing run obtained after 20% clay mixing and the moulding.
By above-mentioned example, Zeolite refrigerating absorbent of the present invention has rate of water absorption and the fast advantage of rate of water loss, so can shorten the operation cycle in the adsorption/desorption balance cycling of refrigeration machine, improves the refrigerating efficiency of unit interval.This refrigerating absorbent fully can substituted freon as a kind of highly effective refrigeration agent.
Claims (5)
1. Zeolite refrigerating absorbent is characterized in that by through Ca ion modification, SiO
2/ Al
2O
3Be 2.5～5.5 Na-faujasite, its each constituent content weight ratio is: Ca ion (in CaO): 0.1～10%:Na ion is (with Na
2The O meter): 2.5～11%; Zeolite: 75～90%; All the other are alumino-silicate adhesive clay or diatomite.
2. the preparation method according to the described Zeolite refrigerating absorbent of claim 1 is characterized in that exchanging with the Ca ion with commodity or synthetic Na-faujasite, and making Ca ion concentration (in the weight of CaO) is 0.1～10% of adsorbent.
3. according to the preparation method of the described Zeolite refrigerating absorbent of claim 2, its feature is by Na in Ca ion-exchange
+/ Ca
++Gram-ion than be proportioning between 2.2～1.8 to add concentration be the calcium saline solution of 0.2～1.0M, carried out ion-exchange 2～4 hours at 80～100 ℃, finish ion-exchange.
4. according to claim 2, the preparation method of 3 described Zeolite refrigerating absorbents is characterized in that calcium salt is calcium chloride or calcium nitrate.
5. application according to the described Zeolite refrigerating absorbent of claim 1 is characterized in that alternative fluorine Lyons makes cold-producing medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95113984 CN1151906A (en) | 1995-12-13 | 1995-12-13 | Zeolite refrigerating absorbent capable of replacing freon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95113984 CN1151906A (en) | 1995-12-13 | 1995-12-13 | Zeolite refrigerating absorbent capable of replacing freon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1151906A true CN1151906A (en) | 1997-06-18 |
Family
ID=5080184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95113984 Pending CN1151906A (en) | 1995-12-13 | 1995-12-13 | Zeolite refrigerating absorbent capable of replacing freon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1151906A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422662C (en) * | 2001-02-21 | 2008-10-01 | 三菱化学株式会社 | Adsorption heat pump and use of adsorbent as adsorbent for adsorption heat pump |
| CN103007884A (en) * | 2012-12-19 | 2013-04-03 | 俞晋高 | Compound sintering zeolite adsorption type refrigeration adsorbing agent and preparation method thereof |
| CN106315614A (en) * | 2016-08-29 | 2017-01-11 | 霍普科技（天津）股份有限公司 | Preparation method of modified Y-type molecular sieve |
-
1995
- 1995-12-13 CN CN 95113984 patent/CN1151906A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422662C (en) * | 2001-02-21 | 2008-10-01 | 三菱化学株式会社 | Adsorption heat pump and use of adsorbent as adsorbent for adsorption heat pump |
| CN103007884A (en) * | 2012-12-19 | 2013-04-03 | 俞晋高 | Compound sintering zeolite adsorption type refrigeration adsorbing agent and preparation method thereof |
| CN106315614A (en) * | 2016-08-29 | 2017-01-11 | 霍普科技（天津）股份有限公司 | Preparation method of modified Y-type molecular sieve |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |