CN102211011B - Integrative preparation method of high-performance adsorbent and metal heat exchange tube - Google Patents
Integrative preparation method of high-performance adsorbent and metal heat exchange tube Download PDFInfo
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- CN102211011B CN102211011B CN 201110151114 CN201110151114A CN102211011B CN 102211011 B CN102211011 B CN 102211011B CN 201110151114 CN201110151114 CN 201110151114 CN 201110151114 A CN201110151114 A CN 201110151114A CN 102211011 B CN102211011 B CN 102211011B
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Abstract
The invention discloses an integrative preparation method of high-performance adsorbent and a metal heat exchange tube. By adopting the preparation method, the heat transfer rate and mass transfer rate can be simultaneously improved. Metal salt, carbonaceous material and metal powder are bonded on the outer wall of a metal tube, multiple holes are formed by activating and carbonizing the carbonaceous material, the mass transfer rate is improved, and the metal salt, the metal powder and the metal tube are tightly connected together by sintering, and the heat transfer rate is enhanced. The metal salt and the metal powder are mixed with a pore-increasing agent or pore-forming agent and then are directly sintered onto the wall of the metal tube. The adsorbent metal salt and the metal tube are tightly combined, the thermal contact resistance of the adsorbent and a heat exchanger is reduced, and an integrative heat exchange tube with the adsorbent is formed. By adopting the heat exchange tube, not only is volume of an adsorption bed and an adsorption refrigerator reduced, but also the difficulty for manufacturing the adsorption refrigerator is greatly reduced.
Description
Technical field
The present invention relates to the absorption refrigeration technical field, particularly a kind of high-performance adsorbent and the incorporate preparation method of metal heat exchanger tube.
Technical background
Therefore the absorption refrigeration technology more and more receives publicity owing to can utilize waste heat and solar energy and utilize working medium free from environmental pollution.But the bottleneck problem that the absorption refrigeration large-scale promotion application is faced is to lack a kind of high performance adsorbent.A most important index of high-performance adsorbent is exactly to have high heat and mass speed, and the adsorbent that has only possessed the high heat transfer mass transfer rate just possibly produce the high adsorption refrigerating device of the little refrigeration performance of volume.At present, commercially available adsorbent is no matter be the requirement that heat transfer property or mass-transfer performance all can not satisfy absorption refrigeration.A lot of scholars improve the method for adsorbent heat and mass in research; But because adsorbent is a porous media; The raising of heat transfer and mass transfer rate often can not realize simultaneously; That is to say that the raising of an index is a cost to sacrifice another index often in heat transfer and these two indexs of mass transfer rate.Such as the adsorbent porosity reaches all the more, and mass transfer rate is just fast more, but rate of heat transfer is just slack-off.Some scholars are through adding the metal of high thermal conductivity or the heat conductivility that expanded graphite improves adsorbent in compound adsorbent; Though this measure has improved the heat conductivility of adsorbent; But mass-transfer performance does not but improve; In addition, do not have absorption property but the material of good heat conductivity, cause effective adsorption component to reduce owing to increased.
Summary of the invention:
To the problem that prior art is conducted heat and mass transfer rate can't improve simultaneously, the invention provides a kind of adsorbent that improves simultaneously and conduct heat and the incorporate metal heat exchanger tube of mass transfer rate and the preparation method of high-performance adsorbent.
The present invention improves the performance of adsorbent from heat transfer and two aspects of mass transfer; Concrete thinking is: adopt slaine as adsorbent, slaine is very big to the adsorbance of water or ammonia, but expands caking in the adsorption process easily; And the heat conductivility of slaine is bad, and mass transfer rate is slow.The present invention improves the heat conductivility of slaine through the mode that adds metal dust, improves mass transfer rate through formation porous in the mixture of slaine and metal dust.Simultaneously, to adsorbent and the bigger problem of heat exchanger thermal contact resistance, the present invention proposes adsorbent and metal tube heat exchanger direct sintering method are together reduced thermal contact resistance.Above-mentioned preparation method can improve the heat transfer and the mass transfer rate of adsorbent simultaneously.
The present invention has dual mode.Concrete steps are following:
The step of first kind of mode is:
1) moulding: raw materials usedly be: slaine, metal dust, carbonaceous material, macromolecule adhesive, said carbonaceous material are wood chip or coconut husk etc. through the raw material of the vegetative fiber composition of pulverizing, with slaine as adsorbent.At first carbonaceous material is immersed in the metal salt solution; The mass ratio of amount of metal salts and carbonaceous material is 4～8: 1; To be impregnatedly carry out drying after fully; And then mix with metal dust, the mixture after mixing is cohered on metal pipe-wall with the macromolecule adhesive, put into die for molding then.
Slaine can be a calcium chloride, a kind of in strontium chloride, magnesium chloride or the barium chloride.Metal dust can be copper powder or aluminium powder.The mass ratio of slaine and metal dust is 20～80%: 80%～20% (slaine carries out drying after being impregnated in the carbonaceous material, and after the drying, the quality that gross mass deducts carbonaceous material is the quality of slaine, and then mixes with metal dust in proportion).The use of said macromolecule adhesive can be adopted prior art.
2) pore-creating: the metal tube after the moulding is put into the carbonization-activation stove, carry out carbonization-activation pore-creating.
The carbonization-activation temperature is 400～900 ℃.
3) sintering: last, metal tube is put into Muffle furnace or sintering furnace carries out sintering, sintering temperature is selected according to the fusing point of used metal dust and slaine, with slaine and metal powder sintered on metal pipe-wall.
The step of the second way is:
1) moulding: raw materials used is slaine, metal dust, macromolecule pore creating material or pore forming agent, macromolecule adhesive; Slaine, metal dust and pore creating material are mixed; Mixture after mixing is cohered on metal pipe-wall with the macromolecule adhesive, put into die for molding then.Slaine can be a calcium chloride, a kind of in strontium chloride, magnesium chloride or the barium chloride.Metal dust can be copper powder or aluminium powder.The mass ratio of slaine and metal dust is 20～80%: 80%～20%.The use of said pore creating material or pore forming agent can be adopted prior art.
2) sintering: the metal tube of moulding is put into Muffle furnace or sintering furnace carries out sintering, and sintering temperature is selected according to the fusing point of used metal dust and slaine, with slaine and metal powder sintered on metal pipe-wall.
First kind of mode adopts the carbonization-activation carbonaceous material to carry out pore-creating; Be specially slaine, carbonaceous material, metal dust are cohered on the metal tube outer wall; Through activation charing carbonaceous material to form flourishing pore structure; Improve mass transfer, through sintering slaine, metal dust and metal tube have been linked together closely then, strengthened heat transfer.In the said process, the charing carbonaceous material is used for pore-creating, improves mass transfer through forming flourishing hole.Metal dust and slaine sintering on metal pipe-wall, because the existence of metal dust, have been improved the heat conductivility of adsorbent slaine.
The second way is carried out pore-creating through adding pore creating material or pore forming agent; This kind mode no longer needs carbonaceous material; The step that does not also need the carbonization-activation carbonaceous material only needs slaine, metal dust and pore creating material are mixed, and directly coheres the back sintering then on metal pipe-wall.So both can form the flourishing compound adsorbent of hole, can slaine and metal tube have been combined closely through sintering again, reduce the thermal contact resistance of adsorbent and heat exchanger.
The adhesive of being selected for use in the dual mode is macromolecular material, in the carbonization-activation process, does not decompose, and divides in the sintering stage and takes off.
The present invention with adsorbent slaine and metal dust direct sintering on metal pipe-wall; Reduced the thermal contact resistance of adsorbent and heat exchanger; Improved heat transfer property, formed a kind of incorporate metal heat exchanger tube that has adsorbent, this kind heat exchanger tube can be used to make adsorption refrigerating device very easily; Only need the heat exchanger tube of a plurality of band adsorbents to be connected promptly and can form adsorbent bed, can effectively reduce the volume of adsorption refrigerating device with elbow.
The present invention's five big advantages technically are:
(1) mass transfer rate is high.Through in slaine, forming flourishing pore structure, improved mass transfer;
(2) good heat-transfer.Improved the heat conductivility of slaine through the adding metal dust;
(3) thermal contact resistance of adsorbent and heat exchanger is little.Method through sintering has reduced the thermal contact resistance of adsorbent and heat exchanger greatly with slaine and metal powder sintered on metal pipe-wall.
(4) absorption property is high.Through the adsorbent of the present invention's preparation, the content of slaine is high, can reach about 80%, and effectively adsorption component content is high, and again because heat and mass speed is fast, so the adsorbance of unit mass adsorbent is big, can reduce the volume of adsorption refrigerating device.
(5) easy to use.The present invention has prepared a kind of heat exchanger tube that has adsorbent, during use, only needs with elbow the heat exchanger tube of a plurality of band adsorbents to be connected promptly and can form adsorbent bed, has reduced the difficulty of processing of refrigeration machine, can effectively reduce the volume of adsorption refrigerating device simultaneously.
Description of drawings
Fig. 1 is the embodiment of the invention 1 process chart;
Fig. 2 is the embodiment of the invention 2 process charts.
The specific embodiment
Below in conjunction with embodiment content of the present invention is described further.
Embodiment one
Adopt the preparation scheme of carbonization-activation carbonaceous material, process route is as shown in Figure 1.
(1) wood chip is impregnated in the metal salt solution, flooded 24 hours.
Wood pellet diameter 0.01mm～1mm, the metal salt solution mass concentration is 40～65%.Slaine can be a calcium chloride, a kind of in strontium chloride, magnesium chloride or the barium chloride.The mass ratio of slaine and wood chip is 4～8: 1
(2) wood chip and the metal salt mixture after will flooding carried out drying, no longer changes until weight.
(3) dried wood chip and metal salt mixture are mixed with metal dust, metal dust can be copper powder or aluminium powder.
The particle diameter of metal dust is between 50～800 orders.The mass ratio of slaine and metal dust is 20～80%: 80%～20%.
(4) evenly mix with above-mentioned wood chip, slaine and metal dust with adhesive (like resin or polyvinyl alcohol).The mass ratio of adhesive is 1%～6% of slaine and a metal powder mixture gross mass.
(5) mixture in (4) is cohered on the metal tube outer wall, such as copper pipe or aluminum pipe.After cohering, in special mould, be pressed.
(6) metal tube that coheres mixture after the moulding is put into the carbonization-activation stove, under 400～900 ℃ of temperature, wood chip is carried out carbonization-activation pore-creating.The carbonization-activation temperature is decided according to the kind of wood chip.
(7) behind the carbonization-activation, the metal tube that will have a mixture is put into 400～900 ℃ Muffle furnace or sintering furnace and is carried out sintering, with slaine and metal powder sintered on metal pipe-wall.Sintering temperature is considered the fusing point of slaine and metal dust.
Embodiment two
Adopt pore creating material or pore forming agent to carry out pore-creating, process route is as shown in Figure 2.
(1) metal dust and metal salt powder are mixed.Metal dust can be copper powder or aluminium powder, and the particle diameter of metal dust is between 50～800 orders.Slaine can be a calcium chloride, a kind of in strontium chloride, magnesium chloride or the barium chloride.The mass ratio of slaine and metal dust is 20～80%: 80%～20%.
(2) said mixture is mixed with pore creating material or pore forming agent.Pore creating material or pore forming agent are at least a in carbonic hydroammonium, ammonium sulfate, organic fiber or the methylcellulose.The mass ratio of pore creating material or pore forming agent is 0.1%～5% of slaine and a metal powder mixture gross mass.
(3) mixture in (2) step is cohered on metal tube, put into particular manufacturing craft compression moulding together.
(4) metal tube of compression moulding band mixture is put into Muffle furnace or sintering furnace carries out sintering under 400～900 ℃ of temperature.
Claims (4)
1. high-performance adsorbent and the incorporate preparation method of metal heat exchanger tube is characterized in that comprising the steps:
1) moulding: raw materials usedly be: slaine, metal dust, carbonaceous material, macromolecule adhesive, said slaine is selected from calcium chloride, a kind of in strontium chloride, magnesium chloride or the barium chloride, said metal dust is copper powder or aluminium powder; At first carbonaceous material is immersed in the metal salt solution, the mass ratio of amount of metal salts and carbonaceous material is 4～8:1; To be impregnatedly carry out drying after fully, and then mix with metal dust, the mass ratio of slaine and metal dust is 20～80%:80%～20%; Mixture after mixing is cohered on metal pipe-wall with the macromolecule adhesive, put into die for molding then;
2) pore-creating: the metal tube after the moulding is put into the carbonization-activation stove, carry out carbonization-activation pore-creating;
3) sintering: last, metal tube to be put into sintering furnace carry out sintering, sintering temperature is selected according to the fusing point of used metal dust and slaine, with slaine and metal powder sintered on metal pipe-wall.
2. high-performance adsorbent as claimed in claim 1 and the incorporate preparation method of metal heat exchanger tube is characterized in that said carbonaceous material is the raw material through the vegetative fiber composition of pulverizing.
3. high-performance adsorbent as claimed in claim 2 and the incorporate preparation method of metal heat exchanger tube is characterized in that said carbonaceous material is wood chip or coconut husk.
4. high-performance adsorbent and the incorporate preparation method of metal heat exchanger tube is characterized in that comprising the steps:
1) moulding: raw materials used is slaine, metal dust, pore creating material, macromolecule adhesive, and said slaine is selected from calcium chloride, a kind of in strontium chloride, magnesium chloride or the barium chloride, and said metal dust is copper powder or aluminium powder; Slaine, metal dust and pore creating material are mixed, and the mass ratio of slaine and metal dust is 20～80%:80%～20%; Mixture after mixing is cohered on metal pipe-wall with the macromolecule adhesive, put into die for molding then;
2) sintering: the metal tube of moulding is put into sintering furnace carry out sintering, sintering temperature is selected according to the fusing point of used metal dust and slaine, with slaine and metal powder sintered on metal pipe-wall.
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| CN103526064A (en) * | 2013-10-11 | 2014-01-22 | 昆明理工大学 | Preparation method for foamy copper |
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| CN201101934Y (en) * | 2007-09-05 | 2008-08-20 | 先普半导体技术(上海)有限公司 | Safe small flow gas purification device |
| CN101274266A (en) * | 2007-12-19 | 2008-10-01 | 华东理工大学 | Method for preparing zeolite molecular sieve single finned tube for sintering shell type adsorbent bed |
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| JP4821563B2 (en) * | 2006-10-31 | 2011-11-24 | 株式会社デンソー | Adsorption module and method of manufacturing adsorption module |
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| CN201101934Y (en) * | 2007-09-05 | 2008-08-20 | 先普半导体技术(上海)有限公司 | Safe small flow gas purification device |
| CN101274266A (en) * | 2007-12-19 | 2008-10-01 | 华东理工大学 | Method for preparing zeolite molecular sieve single finned tube for sintering shell type adsorbent bed |
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