CN109827460B - Nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger and preparation method thereof - Google Patents
Nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger, which comprises a finned tube heat exchanger, wherein a coating formed by a composite drying agent is arranged on the surface of the finned tube heat exchanger; the composite desiccant comprises nano silver powder, zeolite-like molecular sieve and binder. The invention also discloses a preparation method thereof, which comprises the following steps: preparing an acidified binder solution by using an alcohol solvent, a binder, water and acetic acid; adding nano silver powder and zeolite-like molecular sieve into the acidified binder solution, and mixing to obtain a composite suspension; degreasing, degreasing and drying the surface of the finned tube heat exchanger, immersing the finned tube heat exchanger into an acidified binder solution, and taking out the finned tube heat exchanger for curing; and immersing the cured heat exchanger into the composite suspension, and finally drying. The method can improve the heat-conducting property, the equilibrium adsorption property and the adsorption-desorption cycle property of the product.
Description
Technical Field
The invention relates to the field of dehumidification heat pump air conditioning systems, in particular to a nanometer silver powder doped zeolite molecular sieve composite dehumidification heat exchanger and a preparation method thereof.
Background
In recent years, the efficient compact dehumidification heat pump air-conditioning system based on the dehumidification heat exchanger (drying agent is coated on the outer surface of the compact heat exchanger) can overcome the defects of temperature rise and dehumidification of the rotary dehumidification air-conditioning system, can reduce the temperature of a driving heat source, improves the system performance, and has huge energy-saving benefits. The adsorption and regeneration performance of the dehumidification heat exchanger coating has an important influence on the dehumidification performance of the system. The search of the prior art shows that silica gel with stable performance, safety and no toxicity and a composite silica gel desiccant modified by hygroscopic salt are often used for a dehumidification heat exchanger system: an Experimental induction on a purified preparation unit using a-tube heat exchanger with a silica gel coating (2014,63(1):52-58) published by Zhao et al in Applied Thermal Engineering and an Experimental induction and analysis of a compounded silica-gel coated in-tube heat exchangers (2015,51: 169) published by Jiang et al in International Journal of Refraction. Wherein, silica gel mainly has the following defects: firstly, the water vapor adsorption capacity is small, and the adsorption efficiency is low; secondly, the cyclic regeneration temperature is high, and the cyclic regeneration needs a heat source above 70 ℃; thirdly, the heat conductivity is low, and the silica gel is easy to crack after absorbing water. After the composite silica gel is modified by hygroscopic salt, the adsorption performance is improved by times, but higher regeneration temperature is needed, and the problems of low thermal conductivity and easy cracking of the silica gel after moisture absorption still exist. In addition, the impregnated salt particles are subjected to excessive moisture absorption and liquification under a high-humidity working condition, and the hidden trouble of corrosion of a system exists. In view of the above, a new type of zeolite-like molecular sieve such as iron aluminophosphate, which can be regenerated using a low temperature heat source of about 50 ℃, is being attempted for use in a dehumidification heat exchanger system: SAPO-34 coated adsorbent exchange for adsorbent exchange cartridges (2015.82(5):1-7) published by Freni et al in Applied Thermal Engineering, and Performance study of SAPO-34 and FAPO-34 surfactants for purified adsorbent exchange systems (2015.93, Part 1:88-94) published by applicant himself in Energy. However, the materials still have the problems of low cyclic moisture absorption and low thermal conductivity.
Disclosure of Invention
The invention aims to solve the technical problem of providing a composite dehumidifying heat exchanger of a nano silver powder doped zeolite molecular sieve and a preparation method thereof.
In order to solve the technical problem, the invention provides a nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger which comprises a finned tube heat exchanger, wherein a coating formed by a composite drying agent is arranged on the surface of the finned tube heat exchanger; the composite desiccant comprises nano silver powder, zeolite-like molecular sieve and a binder.
The invention also provides a preparation method of the composite dehumidifying heat exchanger of the nano silver powder doped zeolite molecular sieve, which comprises the following steps:
1) and preparing an acidified binder solution:
the binder solution consists of the following components in volume content: 5-70% of alcohol solvent, 5-20% of binder and the balance of water;
adding acetic acid into the binder solution and uniformly stirring until the pH value of the obtained acidified binder solution is 4 +/-0.1;
2) adding nano silver powder and zeolite-like molecular sieve into the acidified binder solution, and mixing to obtain a composite suspension;
the nano silver powder: the zeolite-like molecular sieve is in a mass ratio of 1: 10-50;
adding 1-5 g of nano silver powder into every 20ml of binder solution;
3) after the surface of the finned tube heat exchanger is subjected to deoiling, degreasing and drying treatment (which is a conventional process), immersing the surface of the finned tube heat exchanger into an acidified binder solution for 1-3 minutes, and then taking out the surface of the finned tube heat exchanger for curing;
4) immersing the cured heat exchanger obtained in the step 3) into the composite suspension obtained in the step 2), wherein the immersion time is 1-3 minutes;
and taking out the heat exchanger after soaking, and drying to obtain the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger.
The surface of the nano silver powder doped zeolite-like molecular sieve composite dehumidifying heat exchanger is coated with a composite desiccant, namely, the surface of the finned tube heat exchanger is provided with a coating formed by the composite desiccant, and the composite desiccant consists of the nano silver powder, the zeolite-like molecular sieve and a binder.
As an improvement of the preparation method of the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger, the drying in the step 4) is as follows:
firstly, customizing a drying mold: according to the length, the width and the height of the finned tube heat exchanger, respectively amplifying according to the proportion of 1.2 times, customizing a stainless steel cuboid shell-shaped container with 5 closed surfaces and an opening on one side surface (1 surface corresponding to the width and the height), and then digging a hole on the top surface (1 surface corresponding to the length and the width) of the container, wherein the center of the hole is coincided with the center of the top surface of the container; the size of the hole is equal to the size of the finned tube heat exchanger (i.e., the size of the cross section of the finned tube heat exchanger).
Placing the heat exchanger taken out after soaking into the container from the opening on the side surface of the container, and enabling the finned tube heat exchanger to be opposite to the hole on the top surface of the container, so that the same distance is kept between the finned tube heat exchanger and the side wall of the shell of the container; and then drying is carried out.
This way it is eventually ensured that the surface of the finned tube heat exchanger forms a uniform coating.
As a further improvement of the preparation method of the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger,
the binder is a silane coupling agent;
the silane coupling agent is propyl trimethoxy silane;
the alcohol solvent is at least one of methanol, ethanol and isopropanol;
the zeolite-like molecular sieve is FAPO-34 (which is iron aluminum phosphate with the average pore diameter of 1.8 nm).
The preparation method of the nanometer silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger is further improved as follows:
the curing in the step 3) is carried out at 60-80 ℃ for 0.5-1 h.
The preparation method of the nanometer silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger is further improved as follows:
and in the step 4), drying for 2-12 h at 80-120 ℃.
The preparation method of the nanometer silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger is further improved as follows:
the particle size of the nano silver powder is 60-80 nm.
As a further improvement of the preparation method of the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger,
the uniform mixing in the step 2) is stirring, ultrasonic treatment and secondary stirring in sequence.
Compared with the prior art, the invention has the following beneficial effects:
1) compared with a silica gel dehumidification heat exchanger, the adsorption performance of the coating of the nano silver powder doped zeolite molecular sieve composite dehumidification heat exchanger is remarkably improved by 65% to the maximum;
2) the thermal conductivity of the nano silver powder doped zeolite molecular sieve composite aluminum dehumidifying sheet can be 1.6 times higher than that of a pure zeolite molecular sieve dehumidifying sheet; the thermal conductivity of the nano silver powder doped zeolite molecular sieve composite aluminum desiccant sheet can be 7 times higher than that of a pure silica gel aluminum desiccant sheet.
3) The nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger can be recycled under a lower heat source, and the regeneration temperature can be 10 ℃ lower than that of a pure zeolite molecular sieve dehumidifying heat exchanger under the condition of the same recycling moisture removal rate.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic view of the structure of a mold used in the present invention;
fig. 2 is a scanning electron microscope image of the coating of the composite dehumidifying heat exchanger doped with silver nanopowder and zeolite molecular sieve according to the present invention (example 1).
Detailed Description
The following examples illustrate the invention in detail: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
In the following cases:
the zeolite-like molecular sieves used are all FAPO-34 (iron aluminum phosphate, with an average pore diameter of 1.8 nm); available from mitsubishi chemical stock control.
The particle size of the nano silver powder is 60-80 nm.
In the present invention, it is not explicitly reported that the reaction is carried out at room temperature.
Example 1, the preparation of the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger sequentially comprises the following steps:
1) preparing an acidified binder solution:
uniformly mixing water with volume fraction of 90%, 5% ethanol and 5% propyl trimethoxy silane to obtain a binder solution;
dripping acetic acid into the binder solution, adjusting the pH to 4, and magnetically stirring at room temperature of about 25 ℃ for 4 hours to obtain an acidified binder solution;
dividing the acidified binder solution into 2 parts as required, and using in the following steps 2) and 3), respectively;
2) respectively adding 1g of nano silver powder and 50g of zeolite-like molecular sieve into 20ml of acidified binder solution, and stirring (the stirring time is about 15 minutes), performing ultrasonic treatment (the ultrasonic treatment time is about 15 minutes), and stirring again (the stirring time is about 15 minutes); thereby realizing uniform mixing and obtaining composite turbid liquid;
nano silver powder: zeolite-like molecular sieve is 1:50 in mass ratio;
3) the finned tube heat exchanger is firstly subjected to conventional deoiling, degreasing and drying treatment, and the method specifically comprises the following steps: soaking the finned tube heat exchanger in 0.1mol/L sodium hydroxide solution for 2 minutes to remove grease, washing with water (until the washing solution is neutral), then washing with ethanol (until the washing solution does not contain water), and finally drying at 80 ℃ for 30 minutes;
immersing the finned tube heat exchanger subjected to drying treatment in an acidified binder solution for 2 minutes; taking out and then curing (drying) in an oven at 80 ℃ for half an hour;
4) immersing the cured heat exchanger obtained in the step 3) into the composite suspension obtained in the step 2), wherein the immersion time is 2 minutes;
and taking out the heat exchanger after soaking, wherein the heat exchanger after being taken out must be placed in a die which is customized according to the size of the heat exchanger in advance to be dried in order to ensure that the coating can be uniformly coated on the surface of the heat exchanger.
As shown in fig. 1, the mold customization mode is as follows: according to the length, the width and the height of a heat exchanger (a finned tube heat exchanger), respectively amplifying according to the proportion of 1.2 times, customizing a stainless steel cuboid shell-shaped container with 5 closed surfaces and an opening on one side surface (1 surface corresponding to the width and the height), and then digging a hole on the top surface (1 surface corresponding to the length and the width) of the container, wherein the center of the hole is superposed with the center of the top surface of the container; the size of the hole is the size of the heat exchanger (i.e., the size of the cross-section of the heat exchanger).
And (3) putting the heat exchanger after being taken out into a stainless steel cuboid container from an opening on the side surface of the container, and enabling the heat exchanger to be over against the hole on the top surface of the container, so that the same interval between the heat exchanger and the side wall of the shell of the container is ensured, and finally, the coating can be uniformly coated on the surface of the heat exchanger.
Drying and curing the mold provided with the heat exchanger in a drying oven at 120 ℃ for 4 hours to obtain a nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger; the surface of the nano silver powder doped zeolite-like molecular sieve composite dehumidifying heat exchanger is coated with a composite desiccant, namely, the surface of the finned tube heat exchanger is provided with a coating formed by the composite desiccant (the nano silver powder, the zeolite-like molecular sieve and the binder).
Experiment one, detecting the heat conducting performance, the equilibrium adsorption performance and the adsorption-desorption cycle performance of the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger obtained in example 1:
1. and (3) detecting the heat conducting property:
and randomly shearing a piece of dehumidification aluminum sheet from the nano silver powder doped zeolite molecular sieve composite dehumidification heat exchanger, and measuring the heat conductivity coefficient of the sample by adopting a flash method heat conduction analyzer. The analyzer uses the principle of a laser flash method, uses a xenon lamp to emit a beam of pulse to hit the lower surface of a sample, measures the corresponding temperature rise of the upper surface of the sample through an infrared detector, and obtains the thermal diffusion coefficient and the thermal conductivity coefficient of the sample through fitting calculation.
The tested heat conductivity coefficient of the composite aluminum sheet dehumidified by the nano silver powder doped zeolite molecular sieve is 14.5W/(mK), and the heat diffusion coefficient and the heat conductivity coefficient of the pure zeolite molecular sieve dehumidified aluminum sheet are 9.4W/(mK). Therefore, compared with the pure zeolite molecular sieve dehumidifying aluminum sheet, the heat conductivity coefficient of the composite dehumidifying aluminum sheet is 54 percent higher.
2. And (3) detecting the equilibrium adsorption performance:
setting a constant temperature and constant humidity box at a certain working condition, putting the nano silver powder doped zeolite molecular sieve composite dehumidifying aluminum sheet cut randomly into the constant temperature and constant humidity box to perform an adsorption performance detection experiment, weighing by an electronic balance to perform timing measurement until the adsorption is balanced, and comparing the silica gel dehumidifying aluminum sheet with the pure zeolite molecular sieve dehumidifying aluminum sheet. Adsorption equilibrium was considered when the relative change in measured weight was less than 5% at 30min intervals. Under the working conditions that the adsorption temperature is 20 ℃ and the relative humidity is 70 percent RH, the equilibrium adsorption capacity of the nano silver powder doped zeolite molecular sieve composite dehumidifying aluminum sheet, the silica gel dehumidifying aluminum sheet and the pure zeolite molecular sieve dehumidifying aluminum sheet is 0.185g/g, 0.112g/g and 0.194 g/g. Therefore, compared with silica gel dehumidification aluminum sheets, the dehumidification aluminum sheets of the composite material of the nano silver powder doped zeolite molecular sieve are improved by 65 percent and reduced by 5 percent.
3. And (3) detecting the adsorption-desorption cycle performance:
in the actual operation process, through the switching of the air duct and the refrigerant, the desiccant on the surface of the dehumidification heat exchanger can undergo the periodic alternate processes of adsorption and desorption. In a constant temperature and humidity box, a moisture absorption-desorption cycle working condition test is carried out on the nano silver powder doped zeolite molecular sieve composite dehumidifying aluminum sheet, so that the dehumidifying performance of the efficient compact dehumidifying heat pump air-conditioning system based on the dehumidifying heat exchanger in the actual operation process can be better reflected. The adsorption condition is still 20 ℃ and 70% RH, and the desorption condition is respectively 45 ℃, 25% RH, 55 ℃ and 25% RH. The adsorption and desorption time is respectively half an hour. When the desorption working condition is 45 ℃ and 25% RH, the circulating dehumidification rate of the nano silver powder doped zeolite molecular sieve composite aluminum dehumidification sheet is 0.071g/g, and the circulating dehumidification rate of the pure zeolite molecular sieve composite aluminum dehumidification sheet is 0.073g/g respectively, and the difference between the circulating dehumidification rates is small. When the desorption working condition is 55 ℃ and 25% RH, the circulating dehumidification rate of the nano silver powder doped zeolite molecular sieve composite dehumidification aluminum sheet is 0.126g/g, and the circulating dehumidification rate of the pure zeolite molecular sieve dehumidification aluminum sheet is 0.108g/g respectively, which is improved by 17%.
Remarks explanation: silica gel desiccant aluminum sheet, according to the Experimental study on silica gel-LiCl composite for the purification of composite heat exchange method preparation;
the pure zeolite molecular sieve desiccant aluminum sheet is prepared according to the dipping coating method of Performance study of SAPO-34 and FAPO-34 detergents for purified zeolite coated exchange systems.
Example 2, preparation of a nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger:
1) preparing an acidified binder solution:
the same as in example 1.
2) Respectively adding 2g of nano silver powder and 50g of zeolite-like molecular sieve into 20ml of binder solution, and stirring, ultrasonically treating and stirring again to realize uniform mixing to obtain a composite suspension;
nano silver powder: zeolite-like molecular sieve is 1:25 by mass;
step 3) to step 4), equivalent to example 1.
Example 3, preparation of a nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger:
1) preparing an acidified binder solution:
the same as in example 1.
2) Respectively adding 5g of nano silver powder and 50g of zeolite-like molecular sieve into 20ml of binder solution, and stirring, ultrasonically treating and stirring again to realize uniform mixing to obtain a composite suspension;
namely, the nano silver powder: zeolite-like molecular sieve is 1:10 in mass ratio;
step 3) to step 4), equivalent to example 1.
The nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger obtained in the above examples 2 and 3 was tested by the same method as the experiment, and the results are shown in table 1 of the comparative example of example 1.
TABLE 1
As can be seen from table 1, the present invention has the following performance advantages:
compared with a silica gel dehumidification heat exchanger, the balance adsorption performance of the coating of the nano silver powder doped zeolite molecular sieve composite dehumidification heat exchanger is remarkably improved by 65 percent to the maximum;
the thermal conductivity of the nano silver powder doped zeolite molecular sieve composite aluminum dehumidifying sheet can be improved by 1.6 times compared with that of a pure zeolite molecular sieve aluminum dehumidifying sheet to the maximum extent;
thirdly, the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger can be recycled under a lower heat source, and the regeneration temperature can be 10 ℃ lower than that of a pure zeolite molecular sieve dehumidifying heat exchanger under the condition of the same recycling dehumidification amount.
In addition, the inventor finds out in the invention process that: if the use of the mold is cancelled during drying, namely, the heat exchanger taken out after soaking is directly placed into an oven for drying, the coating formed on the surface of the heat exchanger is uneven, and the performance of the product is reduced.
Comparative example 1, the amount of the zeolite-like molecular sieve was kept constant, and the amount of the silver nanoparticles was reduced, thereby making the silver nanoparticles: the mass ratio of the zeolite-like molecular sieve is 1: 80; the rest is equivalent to example 3.
Comparative example 2, the nano silver powder is changed into graphite powder, and the using amount is not changed; the rest is equivalent to example 3.
The composite dehumidifying heat exchanger obtained in the above comparative example was tested in the same manner as in experiment one, and the results are shown in table 2.
TABLE 2
In addition, the inventor also finds that: nano silver powder: when the mass ratio of the zeolite-like molecular sieve is higher than 1:10, the composite dehumidifying heat exchanger doped with the nano silver powder and the zeolite-like molecular sieve is difficult to prepare, and the coating is easy to crack.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (5)
1. The preparation method of the nanometer silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger is characterized by comprising the following steps of:
the composite dehumidification heat exchanger comprises a finned tube heat exchanger, wherein a coating formed by a composite drying agent is arranged on the surface of the finned tube heat exchanger; the composite desiccant comprises nano silver powder, a zeolite-like molecular sieve and a binder;
the preparation method comprises the following steps:
1) and preparing an acidified binder solution:
the binder solution consists of the following components in volume content: 5-70% of alcohol solvent, 5-20% of binder and the balance of water;
adding acetic acid into the binder solution and uniformly stirring until the pH value of the obtained acidified binder solution is 4 +/-0.1;
the binder is a silane coupling agent; the silane coupling agent is propyl trimethoxy silane;
the alcohol solvent is at least one of methanol, ethanol and isopropanol;
2) adding nano silver powder and zeolite-like molecular sieve into the acidified binder solution, and mixing to obtain a composite suspension;
the nano silver powder: the zeolite-like molecular sieve is in a mass ratio of 1: 10-50;
adding 1-5 g of nano silver powder into every 20ml of binder solution;
the zeolite-like molecular sieve is FAPO-34;
3) after the surface of the finned tube heat exchanger is subjected to deoiling, degreasing and drying treatment, the finned tube heat exchanger is immersed in an acidified binder solution for 1-3 minutes and then taken out for curing;
4) immersing the cured heat exchanger obtained in the step 3) into the composite suspension obtained in the step 2), wherein the immersion time is 1-3 minutes;
taking out the heat exchanger after soaking, and drying to obtain the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger; the drying comprises the following steps:
firstly, customizing a drying mold: according to the length, the width and the height of the finned tube heat exchanger, respectively amplifying according to the proportion of 1.2 times, customizing a stainless steel cuboid shell-shaped container with 5 closed surfaces and an opening on one side surface, and then digging a hole on the top surface of the container, wherein the center of the hole is coincided with the center of the top surface of the container; the size of the hole is equal to that of the finned tube heat exchanger;
placing the heat exchanger taken out after soaking into the container from the opening on the side surface of the container, and enabling the finned tube heat exchanger to be opposite to the hole on the top surface of the container, so that the same distance is kept between the finned tube heat exchanger and the side wall of the shell of the container; and then drying is carried out.
2. The method for preparing the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger of claim 1, wherein the method comprises the following steps: the curing in the step 3) is carried out at 60-80 ℃ for 0.5-1 h.
3. The method for preparing the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger as claimed in claim 2, wherein the method comprises the following steps: and in the step 4), drying for 2-12 h at 80-120 ℃.
4. The method for preparing the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger as claimed in claim 3, wherein the method comprises the following steps: the particle size of the nano silver powder is 60-80 nm.
5. The method for preparing the nano silver powder doped zeolite molecular sieve composite dehumidifying heat exchanger according to any one of claims 1 to 4, characterized by comprising the following steps: the uniform mixing in the step 2) is stirring, ultrasonic treatment and secondary stirring in sequence.
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