CN106938189A - The application of nano-sized carbon/expanded graphite chlorate composite adsorbing material - Google Patents
The application of nano-sized carbon/expanded graphite chlorate composite adsorbing material Download PDFInfo
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- CN106938189A CN106938189A CN201710258191.5A CN201710258191A CN106938189A CN 106938189 A CN106938189 A CN 106938189A CN 201710258191 A CN201710258191 A CN 201710258191A CN 106938189 A CN106938189 A CN 106938189A
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- nano
- expanded graphite
- carbon
- chlorate
- adsorbing material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P80/00—Climate change mitigation technologies for sector-wide applications
- Y02P80/10—Efficient use of energy, e.g. using compressed air or pressurized fluid as energy carrier
- Y02P80/15—On-site combined power, heat or cool generation or distribution, e.g. combined heat and power [CHP] supply
Abstract
The invention discloses a kind of composite adsorbing material absorbing refrigeration system, combined power and cooling or or cooling-heating treatment system in application, the composite adsorbing material include 60 parts~70 parts of chlorate；30 parts~40 parts of expanded graphite；1 part~6 parts of nano carbon particle, concrete application method：Composite adsorbing material is packed into adsorbent bed, density of the composite adsorbing material on adsorbent bed is 300 Kg/m3‑600 Kg/m3, bed tempertaure is adsorbed in regulation and the temperature at condensation/vaporization end carries out adsorption and desorption to ammonia, and the adsorption and desorption time is respectively 12 hours.Compared with current chlorate expanded graphite adsorbent, nano-sized carbon/expanded graphite chlorate composite adsorbing material conciliates the rate of adsorption to the rate of adsorption of ammonia has more apparent raising, applied in using the absorbing refrigeration system of chlorate ammonia working medium pair and combined power and cooling system and cooling-heating treatment system based on absorption refrigeration, its absorption refrigeration efficiency can be improved, there is significantly application value in absorption refrigeration field.
Description
Technical field
The invention belongs to absorption type refrigerating field, and in particular to a kind of nano-sized carbon/expanded graphite-chlorate composite adsorption material
Material exists
Application in absorbing refrigeration system and combined power and cooling system or cooling-heating treatment system based on absorption refrigeration.
Background technology
The green refrigeration technology that ammonia adsorptive refrigeration technology drives as a kind of low grade heat energy, with wide application sky
Between, such as solar airconditioning or heat pump, industrial waste heat utilization, fishing boat ice making.Chlorate-ammonia is conventional adsorptionworking pairs,
Transmission by chlorate to heat during the adsorption and de-adsorption of ammonia, is freezed.Mainly pass through absorption refrigeration system at present
The improvement of system and the development of novel adsorption agent material, to promote the development of adsorption refrigeration technique.
Current research is usually that chlorate and graphite, activated carbon etc. are mixed to form into compound adsorbent, such as patent
2004100667810 disclose a kind of calcium-expanding black lead mixed adsorbent, and it is mainly by increasing the thermal conductivity of adsorbent
Refrigerating efficiency can be improved, but the influence that its rate of adsorption to ammonia conciliates the rate of adsorption do not refer to.
The present invention has found that nano-sized carbon/expanded graphite-chlorate composite adsorbing material can be significantly improved to ammonia by studying
The rate of adsorption conciliates the rate of adsorption, therefore this sorbing material is applied in the absorbing refrigeration system using chlorate-ammonia working medium pair
And in the combined power and cooling system or cooling-heating treatment system based on absorption refrigeration, refrigerating efficiency and total system can be improved
Performance.
The content of the invention
It is an object of the invention to provide a kind of nano-sized carbon/expanded graphite-chlorate composite adsorbing material in absorption refrigeration
Application in system, combined power and cooling system or cooling-heating treatment system.
The present invention is achieved by the following technical solutions：
A kind of nano-sized carbon/expanded graphite-chlorate composite adsorbing material is in absorbing refrigeration system, combined power and cooling system or cool and thermal power
Three
Application in production system, the nano-sized carbon/expanded graphite-chlorate composite adsorbing material, by weight, including chlorination
60 parts~70 parts of salt；30 parts~40 parts of expanded graphite；1 part~6 parts of nano carbon particle, it is characterised in that concrete application method is such as
Under：
Adsorbent bed, the nano-sized carbon/swollen will be packed into after nano-sized carbon/expanded graphite-chlorate composite adsorbing material drying water removal
Swollen graphite-bulk density of the chlorate composite adsorbing material on adsorbent bed is 300 Kg/m3-600 Kg/m3, adsorbent bed is with storing
The condensation/vaporization end for having liquid ammonia is connected by pipeline with air valve, generally in air-tight state, and regulation adsorbs bed tempertaure and cold
The temperature of solidifying/evaporation ends carries out adsorption and desorption to ammonia, and the time of adsorption and desorption is respectively 1-2 hours.
The nano carbon particle is carbon nickel coat nano particle, carbon alclad nano particle, carbon- coated iron nanoparticles or carbon bag cobalt
One or more in nano particle, preferably carbon nickel coat nano particle or carbon alclad nano particle.
The chlorate is one in calcium chloride, strontium chloride, manganese chloride, magnesium chloride, barium chloride and other metal chlorides
Plant or several, preferably strontium chloride.
Above-mentioned nano-sized carbon/expanded graphite-chlorate the composite adsorbing material of invention, can make by the following method
It is standby to obtain：
Nano carbon particle is dissolved in ethanol, it is ultrasonically treated 10-30 minutes, expanded graphite is then added, continues ultrasonically treated 10-30
Minute, chlorate is added, is then sonicated 10-30 minutes, obtains mixing suspension, mixing suspension is heated and stirred simultaneously
Mix, ethanol is quickly volatilized, obtain thick object, dry, produce.
The absorbing refrigeration system is the absorbing refrigeration system using chlorate-ammonia working medium pair.
Adsorption and de-adsorption needs certain mass transfer condition, i.e. amino molecule in the access way of sorbing material, if adsorption material
The bulk density of material is too high, then may hinder the turnover of ammonia, causes adsorption and desorption speed to decline, if the body of sorbing material
Product density is too low, and due to the amount of chloride in sorbing material, to be then likely to result in adsorbance very little too low, so as to influence adsorption effect.
It is preferred that, the nano-sized carbon/expanded graphite-bulk density of the chlorate composite adsorbing material on adsorbent bed is 400 Kg/m3 -
500 Kg/m3。
When absorption, the temperature of the adsorbent bed is 10-40 DEG C, and the temperature at the condensation/vaporization end is -30-30 DEG C, excellent
Choosing,
The temperature of the adsorbent bed is 15-30 DEG C, and the temperature at the condensation/vaporization end is 10-20 DEG C.
When desorption, the temperature of the adsorbent bed is 100-300 DEG C, and the temperature at the condensation/vaporization end is -30-30
DEG C, it is excellent
Choosing, the temperature of the adsorbent bed is 110-160 DEG C, and the temperature at the condensation/vaporization end is -20-0 DEG C.Work as desorption
When, when generally absorption bed tempertaure is relatively low, its desorption rate is slower, nano-sized carbon/expanded graphite-chlorate composite adsorption of the invention
Material can make originally due to absorption bed tempertaure it is not high and cause the slower situation of desorption rate be improved significantly.
Under identical quality requirements, the particle diameter of the nano-sized carbon/expanded graphite-chlorate composite adsorbing material is excessive, is difficult
Formation heat transfer network, the too small then easy obstruction mass transfer channel of particle diameter, therefore, nano-sized carbon/expanded graphite-chlorate of the present invention
The particle diameter of composite adsorbing material is 50nm-200nm.
Compared with prior art, the present invention has the advantages that：
It has been investigated that, compared with current chlorate-expanded graphite adsorbent, nano-sized carbon/expanded graphite-chlorate is compound to be inhaled
Enclosure material, which conciliates the rate of adsorption to the rate of adsorption of ammonia, has more apparent raising, of the invention by nano-sized carbon/expanded graphite-chlorate
Composite adsorbing material is applied in the absorbing refrigeration system using chlorate-ammonia working medium pair and the combined power and cooling based on absorption refrigeration
In system or cooling-heating treatment system, its absorption refrigeration efficiency can be improved, has in absorption refrigeration field and significantly applies valency
Value.
Embodiment
Embodiment is given below so that the present invention to be specifically described, but not limited to this.
Embodiment 1：
By carbon nickel coat nano particle, 1.5 parts are dissolved in ethanol, ultrasonically treated 25 minutes, then add 33 parts of expanded graphite, continue super
Sonication 25 minutes, adds 65.5 parts of strontium chloride, is then sonicated 20 minutes, obtains mixing suspension, by mixing suspension
It is put into 75 DEG C of water-baths and heats and stir simultaneously, ethanol is quickly volatilized, obtain thick object, dries, producing particle diameter is
50nm-200nm carbon nickel coat nano particle/expanded graphite-strontium chloride composite adsorbing material.
Adsorbent bed, carbon will be packed into after carbon nickel coat nano particle/expanded graphite-chlorate composite adsorbing material drying water removal
Nickel coat nano particle/expanded graphite-density of the chlorate composite adsorbing material on adsorbent bed is 450Kg/m3, adsorbent bed is with storing
The condensation/vaporization end for having liquid ammonia is connected by pipeline with air valve, generally in air-tight state.
When regulation absorption bed tempertaure is 20 DEG C, the temperature at condensation/vaporization end is 20 DEG C, ammonia is adsorbed, adsorption time
For 80min, test its rate of adsorption and the rate of adsorption of ammonia is averagely about improved than expanded graphite-strontium chloride under the same terms
15%；
When regulation absorption bed tempertaure is 20 DEG C, condensation/vaporization end temperature is -20 DEG C, ammonia is adsorbed, adsorption time is
100min, tests its rate of adsorption and the rate of adsorption of ammonia is averagely about improved than expanded graphite-strontium chloride under the same terms
12%。
Embodiment 2：
When regulation absorption bed tempertaure is 110 DEG C, when condensation/vaporization end temperature is -20 DEG C, desorption is carried out to ammonia, during desorption
Between be 80min, remaining be the same as Example 1 tests desorption of the expanded graphite-strontium chloride to ammonia under its desorption speed ratio the same terms
Attached speed averagely about improves 30%.
When regulation absorption bed tempertaure is 170 DEG C, when condensation/vaporization end temperature is -20 DEG C, desorption, desorption are carried out to ammonia
The attached time is 60min, and remaining be the same as Example 1 tests under its desorption speed ratio the same terms expanded graphite-strontium chloride to ammonia
Desorption speed averagely about improves 3%.
Embodiment 3：
By carbon alclad nano particle, 1.5 parts are dissolved in ethanol, ultrasonically treated 25 minutes, then add 33 parts of expanded graphite, continue super
Sonication 25 minutes, adds 65.5 parts of strontium chloride, is then sonicated 20 minutes, obtains mixing suspension, by mixing suspension
It is put into 75 DEG C of water-baths and heats and stir simultaneously, ethanol is quickly volatilized, obtain thick object, dries, producing particle diameter is
50nm-200nm carbon alclad nano particle/expanded graphite-strontium chloride composite adsorbing material.
Adsorbent bed, carbon will be packed into after carbon alclad nano particle/expanded graphite-chlorate composite adsorbing material drying water removal
Alclad nano particle/expanded graphite-density of the chlorate composite adsorbing material on adsorbent bed is 500 Kg/m3, adsorbent bed with
The condensation/vaporization end for being stored with liquid ammonia is connected by pipeline with air valve, generally in air-tight state.
When regulation absorption bed tempertaure is 20 DEG C, the temperature at condensation/vaporization end is 10 DEG C, ammonia is adsorbed, adsorption time
For 80min, test its rate of adsorption and the rate of adsorption of ammonia is averagely about improved than expanded graphite-strontium chloride under the same terms
12%。
When regulation absorption bed tempertaure is 20 DEG C, condensation/vaporization end temperature is -10 DEG C, ammonia is adsorbed, adsorption time is
100min, tests its rate of adsorption and averagely about improves 9% to the rate of adsorption of ammonia than expanded graphite-strontium chloride under the same terms.
Embodiment 4：
When regulation absorption bed tempertaure is 140 DEG C, when condensation/vaporization end temperature is -20 DEG C, desorption is carried out to ammonia, during desorption
Between be 80min, remaining be the same as Example 3 tests desorption of the expanded graphite-strontium chloride to ammonia under its desorption speed ratio the same terms
Attached speed averagely about improves 21%.
When regulation absorption bed tempertaure is 180 DEG C, when condensation/vaporization end temperature is -20 DEG C, desorption, desorption are carried out to ammonia
The attached time is 60min, and remaining be the same as Example 3 tests under its desorption speed ratio the same terms expanded graphite-strontium chloride to ammonia
Desorption speed averagely about improves 5%.
Embodiment 5：
By carbon- coated iron nanoparticles, 1.5 parts are dissolved in ethanol, ultrasonically treated 25 minutes, then add 33 parts of expanded graphite, continue super
Sonication 25 minutes, adds 65.5 parts of strontium chloride, is then sonicated 20 minutes, obtains mixing suspension, by mixing suspension
It is put into 75 DEG C of water-baths and heats and stir simultaneously, ethanol is quickly volatilized, obtain thick object, dries, producing particle diameter is
50nm-200nm carbon- coated iron nanoparticles/expanded graphite-strontium chloride composite adsorbing material.
Adsorbent bed, carbon will be packed into after carbon- coated iron nanoparticles/expanded graphite-chlorate composite adsorbing material drying water removal
Iron clad nano particle/expanded graphite-density of the chlorate composite adsorbing material on adsorbent bed is 400 Kg/m3, adsorbent bed with
The condensation/vaporization end for being stored with liquid ammonia is connected by pipeline with air valve, generally in air-tight state.
When regulation absorption bed tempertaure is 20 DEG C, the temperature at condensation/vaporization end is 20 DEG C, ammonia is adsorbed, adsorption time
For 80min, test its rate of adsorption and the rate of adsorption of ammonia is averagely about improved than expanded graphite-strontium chloride under the same terms
11%。
When regulation absorption bed tempertaure is 20 DEG C, condensation/vaporization end temperature is 0 DEG C, ammonia is adsorbed, adsorption time is
100min, tests its rate of adsorption and averagely about improves 7% to the rate of adsorption of ammonia than expanded graphite-strontium chloride under the same terms.
Embodiment 6：
When regulation absorption bed tempertaure is 155 DEG C, when condensation/vaporization end temperature is -20 DEG C, desorption is carried out to ammonia, during desorption
Between be 80min, remaining be the same as Example 5 tests desorption of the expanded graphite-strontium chloride to ammonia under its desorption speed ratio the same terms
Attached speed averagely about improves 16%.
When regulation absorption bed tempertaure is 210 DEG C, when condensation/vaporization end temperature is -20 DEG C, desorption, desorption are carried out to ammonia
The attached time is 60min, and remaining be the same as Example 5 tests under its desorption speed ratio the same terms expanded graphite-strontium chloride to ammonia
Desorption speed averagely about improves 3%.
Claims (8)
1. a kind of nano-sized carbon/expanded graphite-chlorate composite adsorbing material is in absorbing refrigeration system, combined power and cooling system or cold and hot
Application in electric three co-generation systems, the nano-sized carbon/expanded graphite-chlorate composite adsorbing material, by weight, including chlorine
60 parts~70 parts of salt dissolving；30 parts~40 parts of expanded graphite；1 part~6 parts of nano carbon particle, it is characterised in that concrete application method
It is as follows：
Adsorbent bed, the nano-sized carbon/swollen will be packed into after nano-sized carbon/expanded graphite-chlorate composite adsorbing material drying water removal
Swollen graphite-density of the chlorate composite adsorbing material on adsorbent bed is 300 Kg/m3-600 Kg/m3, adsorbent bed is with being stored with
The condensation/vaporization end of liquid ammonia is connected by pipeline with air valve, generally in air-tight state, adjust absorption bed tempertaure and condense/
The temperature of evaporation ends carries out adsorption and desorption to ammonia, and the time of adsorption and desorption is respectively 1-2 hours.
2. application according to claim 1, it is characterised in that the nano carbon particle is carbon nickel coat nano particle, carbon bag
One or more in aluminum nanoparticles, carbon- coated iron nanoparticles or carbon bag cobalt nano-particle, preferably carbon nickel coat nano particle or
Carbon alclad nano particle.
3. application according to claim 1, it is characterised in that the chlorate is calcium chloride, strontium chloride, manganese chloride, chlorine
Change the one or more in iron, barium chloride or nickel chloride, preferably strontium chloride.
4. application according to claim 1, it is characterised in that the absorbing refrigeration system is to use chlorate-ammonia working medium
To absorbing refrigeration system.
5. application according to claim 1, it is characterised in that the nano-sized carbon/expanded graphite-calcium chloride composite adsorption material
It is 400 Kg/m to expect the density on adsorbent bed3-500 Kg/m3。
6. application according to claim 1, it is characterised in that when absorption, the temperature of the adsorbent bed is 10-40 DEG C,
The temperature at the condensation/vaporization end is -30-40 DEG C, it is preferred that the temperature of the adsorbent bed is 15-30 DEG C, the condensation/steaming
The temperature of originator is 10-20 DEG C.
7. application according to claim 1, it is characterised in that when desorption, the temperature of the adsorbent bed is 100-300
DEG C, the temperature at the condensation/vaporization end is -30-30 DEG C, it is preferred that the temperature of the adsorbent bed is 110-160 DEG C, described cold
The temperature of solidifying/evaporation ends is -20-0 DEG C.
8. application according to claim 1, it is characterised in that the nano-sized carbon/expanded graphite-chlorate composite adsorption material
The particle diameter of material is 50 nm-200nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554376A (en) * | 2018-04-11 | 2018-09-21 | 上海交通大学 | A kind of salty adsorbent of solid-state and the salty storage ammonia module of solid-state |
| CN111467929A (en) * | 2020-04-15 | 2020-07-31 | 大连海事大学 | Thin gas adsorption and trapping device and adsorption and trapping process and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104896787A (en) * | 2015-01-12 | 2015-09-09 | 上海交通大学 | An adsorption refrigeration device driven by engine exhaust gas |
| CN105202804A (en) * | 2015-09-15 | 2015-12-30 | 广东美的制冷设备有限公司 | Adsorption and vapor compression cascade type refrigeration device and control method thereof |
| CN105498690A (en) * | 2016-01-15 | 2016-04-20 | 广东工业大学 | Composite adsorption material and preparation method thereof |
-
2017
- 2017-04-19 CN CN201710258191.5A patent/CN106938189A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104896787A (en) * | 2015-01-12 | 2015-09-09 | 上海交通大学 | An adsorption refrigeration device driven by engine exhaust gas |
| CN105202804A (en) * | 2015-09-15 | 2015-12-30 | 广东美的制冷设备有限公司 | Adsorption and vapor compression cascade type refrigeration device and control method thereof |
| CN105498690A (en) * | 2016-01-15 | 2016-04-20 | 广东工业大学 | Composite adsorption material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554376A (en) * | 2018-04-11 | 2018-09-21 | 上海交通大学 | A kind of salty adsorbent of solid-state and the salty storage ammonia module of solid-state |
| CN111467929A (en) * | 2020-04-15 | 2020-07-31 | 大连海事大学 | Thin gas adsorption and trapping device and adsorption and trapping process and application thereof |
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Application publication date: 20170711 |