CN103007884A - Compound sintering zeolite adsorption type refrigeration adsorbing agent and preparation method thereof - Google Patents
Compound sintering zeolite adsorption type refrigeration adsorbing agent and preparation method thereof Download PDFInfo
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- CN103007884A CN103007884A CN2012105533855A CN201210553385A CN103007884A CN 103007884 A CN103007884 A CN 103007884A CN 2012105533855 A CN2012105533855 A CN 2012105533855A CN 201210553385 A CN201210553385 A CN 201210553385A CN 103007884 A CN103007884 A CN 103007884A
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 36
- 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 36
- 239000010457 zeolite Substances 0.000 title claims abstract description 36
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005057 refrigeration Methods 0.000 title abstract description 17
- 239000003795 chemical substances by application Substances 0.000 title abstract description 11
- 238000005245 sintering Methods 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 title abstract 5
- 239000000843 powder Substances 0.000 claims abstract description 19
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 14
- 239000004917 carbon fiber Substances 0.000 claims abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 7
- 238000005056 compaction Methods 0.000 claims abstract description 4
- 230000002745 absorbent Effects 0.000 claims description 17
- 239000002250 absorbent Substances 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 29
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000003795 desorption Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229940074155 strontium bromide Drugs 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention discloses a compound sintering zeolite adsorption type refrigeration adsorbing agent and a preparation method thereof. Zeolite, carbon fiber powder and additives are sintered to form the refrigeration adsorbing agent, and the additives are acid liquid, water and a binding agent. The zeolite component is measured in 100 parts by mass, and the refrigeration adsorbing agent comprises components in parts by mass as follows: 100 parts of the zeolite, 10 parts of carbon fibers, 0.8-3 parts of the acid liquid, 1-6 parts of the binding agent and 20-36 parts of water. All components are mixed uniformly, dumped into a mold and subjected to ultrasonography after compaction forming, so that the components are compact; and then the components are demolded, dried in the shade and sintered at a high temperature. According to the compound sintering zeolite adsorption type refrigeration adsorbing agent, heat conduction is enhanced through the high-heat conductivity carbon fibers; the strength is improved through high-temperature sintering and forming; and compared with a common physical accumulation adsorption type refrigeration adsorbing agent, the compound sintering zeolite adsorption type refrigeration adsorbing agent has the advantage that the heat-conducting performance between adsorbing agents is improved by 10 times to 20 times under the condition that the adsorbing performance of the compound sintering zeolite adsorption type refrigeration adsorbing agent is basically unchanged.
Description
Technical field
The present invention relates to the absorption type refrigerating field, be specifically related to a kind of complex sintered type zeolite adsorption formula refrigerating absorbent and preparation method thereof.
Background technology
Adsorptive refrigeration technology uses regenerative resource (such as solar energy, geothermal energy) and low grade residual heat as driving heat source; Utilize adsorbent under different temperatures to cold-producing medium adsorption/desorption action substitution compressor; Used cold-producing medium is the water of environmentally safe, alcohol etc.; Therefore adsorptive refrigeration technology is a kind of Refrigeration Technique of environmental type, matches with the trend of current environmental energy coordinated development, has wide development space.
The basic principle of absorption refrigeration is: the porosu solid adsorbent has suction-operated to refrigerant gas, and adsorption capacity changes with the difference of adsorbent temperature.Periodic cooling and heating adsorption agent make it alternately sorption and desorption.During desorb, discharge refrigerant gas, and solidifyingly in condenser be liquid; During absorption, the refrigerant liquid evacuator body in the evaporimeter produces cold.
But in the process of practical application, adsorptive refrigeration technology still has some problems that need to solve.Wherein the performance of adsorbent is huge on the refrigeration impact, good adsorbent generally has following several requirement: a. good heat-transfer, rapid with the heat transfer of fluid, can effectively overcome simultaneously the impact of adsorbent low thermal conductivity, the guarantee adsorbent in time replenishes the needed heat of desorption of desorption process and in time takes away the heat of adsorption that adsorption process is emitted like this, and it is to make adsorbent have high performance necessary condition.B. mass transfer is rapid, and the adsorbent diffusion admittance is unimpeded, and the desorption rate of the adsorption rate of guarantee adsorption process and desorption process shortens cycle period like this, improves the refrigeration work consumption of unit working medium.The ratio of c. filling the thermal capacitance of adsorbent in the thermal capacitance of heating agent fluid itself and the bed has also determined the performance of adsorption refrigeration system.This mainly is because the heating and cooling of adsorbent itself can cause a large amount of system thermal losses, has had a strong impact on the performance of system.
Mentioned a kind of high temperature type absorbent that is formed by strontium bromide, strontium chloride and additive in the patent of publication number CN1001385965A, have higher heat conductivility and reach preferably high temperature adsorption performance, the phenomenon of desorption powder injection is suppressed, and desorb and adsorption capacity obviously improve.But it adopts poisonous ammonia as cold-producing medium, and certain danger is arranged.
Mentioned a kind of preparation technology of sintering type zeolite molecular sieve adsorption refrigeration unit tube in the Chinese patent of publication number CN1011144664A.This preparation technology has improved the thermal conductivity factor of molecular sieve, reduces the thermal contact resistance between molecular sieve and metal wall, thereby strengthens the heat transfer of adsorbent bed.This patent utilization sintering improves the thermal conductivity factor of molecular sieve, although greatly improve than simple bulk property, raising still has certain limitation to heat conductivility near sintering.
Summary of the invention
The invention provides a kind of complex sintered type zeolite adsorption formula refrigerating absorbent and preparation method thereof, this preparation technology has improved the thermal conductivity factor of adsorbent, and does not affect the absorption property of adsorbent.
A kind of complex sintered type zeolite adsorption formula refrigerating absorbent comprises zeolite, carbon fiber powder and additive, and described zeolite is 13X type molecular sieve, and its aperture 10A can adsorb any molecule less than 10A, has higher fail temperature, particle diameter 1 ~ 1.6mm; Described carbon fiber is high heat-conducting type, and the thermal conductivity factor on machine direction can surpass copper, can reach 700w/ (mk), diameter 10 μ m, long 200 μ m; Described additive is acid solution, water and binding agent;
Take the mass parts of zeolite as 100 parts, made by the raw material of following mass parts:
100 parts in zeolite
5～10 parts of carbon fiber powders
0.8 ~ 3 part of acid solution
1 ~ 6 part of binding agent
10 ~ 26 parts in water
Described acid solution is nitric acid, and the concentration of nitric acid is 2 ~ 10%;
Described binding agent is sodium carboxymethylcellulose and polyethylene glycol oxide, wherein the mass ratio of sodium carboxymethylcellulose (CMC) and polyethylene glycol oxide (PEO) is 1:0.4 ~ 4, the mean molecule quantity of PEO is 300 ~ 4,000,000, have that ash content is low, decomposition temperature is low, the alkali metal impurity ion concentration low advantage larger to glass part performance impact, with sodium carboxymethylcellulose (CMC) when being used, PEO for liquid phase, CMC for solid phase, both are in conjunction with having extraordinary caking property, the adsorbent blank is combined closely, be difficult for disperseing.
The invention provides a kind of preparation method of complex sintered type zeolite adsorption formula refrigerating absorbent, comprising:
(1) in proportion zeolite, carbon fiber powder are dry mixed to get solid powder;
(2) in described solid powder, add acid solution in proportion, mix; Then add in proportion binding agent and water, mix; Then pour mixture into mould, compaction moulding; Then utilize ultrasonic echography to eliminate space between the particle;
(3) after the final drying, high-temperature calcination forms by a firing.
Preferably, described to be dry mixed the time be 20 ~ 30min, and described mould can be made cylindric or square casing according to the demand of actual adsorbent bed; Described ultrasonic time is 20 ~ 30min; The final temperature of described drying is 55 ~ 65 ℃; The final temperature of described calcining is 430 ~ 500 ℃, and 80 ℃/h of calcining heating rate keeps 4 h after the arrival maximum temperature.
The complex sintered type zeolite adsorption formula refrigerating absorbent of the present invention preparation is changed the mode that original physics is piled up, and adopts bonding agent that absorbent particles is bonded together, and connects closelyr between the particle, and the conduction of heat is rapider; Behind the adsorbent sintering adhesive bonding, intensity improves, in the repeatedly not easily broken dispersion impact absorption of adsorption-desorption process and heat transfer; Next adopts the carbon fiber powder of a small amount of high heat conduction as heat carrier, strengthens the transmission of heat in adsorbent, does not affect the absorption property of adsorbent simultaneously.
The complex sintered type zeolite adsorption formula refrigerating absorbent of the present invention preparation is compared with the absorption type refrigerating adsorbent that General Physics is piled up, and in the substantially constant situation of its absorption property, the heat conductivility between the adsorbent has improved 10 ~ 20 times.
Description of drawings
Fig. 1 is the preparation flow figure of complex sintered type zeolite adsorption formula refrigerating absorbent.
The specific embodiment
The raw materials used commercially available prod that is.
Embodiment 1
The preparation of complex sintered type zeolite adsorption formula refrigerating absorbent:
(1) taking by weighing zeolite raw material 100g, carbon fiber powder 10g is dry mixed 20 ~ 30min and gets solid powder;
(2) take by weighing 3% nitric acid acid solution 1 g and pour solid powder into, mix;
(3) take by weighing sodium carboxymethylcellulose 1 g and polyethylene glycol oxide 4 g, in 10 g hot water, after the dissolving, pour solid powder into, slowly add and mix;
(4) pour mixture into mould, compaction moulding;
(5) ultrasonic 20-30 min eliminates space between the particle;
(6) demoulding places 60 ℃ baking oven with the raw material of moulding, low temperature drying 24-48 h;
(7) fire, the shaping raw material that drying is good is put into Muffle furnace and is fired, 80 ℃/h of heating rate, and final temperature is got 500 ℃, keeps 4 h after the arrival maximum temperature, finally obtains adsorbent finished product 110 g.
The effective thermal conductivity of this adsorbent is 0.811 w/ (mk) after testing, compares with the zeolite type adsorbent that common physics is piled up, and has improved 10 ~ 20 times.The mechanical strength of adsorbent is than Gao Keda 120.2N/cm, and is repeatedly in the adsorption/desorption process, not easily broken.Absorption property is compared with the zeolite raw material, only descends 7 ~ 8%, and the saturated adsorption rate can reach 33.45%.
Embodiment 2
Change the carbon fiber powder quality among the embodiment 1 into 5g, concentration of nitric acid changes 1% into, and other conditions are constant, finally makes adsorbent finished product 113.6g.The effective thermal conductivity of adsorbent is 0.281w/ (mk) after testing, and mechanical strength is than Gao Keda 140.9 N/cm, and the saturated adsorption rate can reach 34.75%.
Embodiment 3
Change the polyethylene glycol oxide quality among the embodiment 1 into 1g, concentration of nitric acid changes 1% into, and other conditions are constant, finally makes adsorbent finished product 113.6g.The effective thermal conductivity of adsorbent is 0. 756w/ (mk) after testing, and mechanical strength is than Gao Keda 97.1 N/cm, and the saturated adsorption rate can reach 35.95%.
Claims (6)
1. a complex sintered type zeolite adsorption formula refrigerating absorbent is formed by a firing by zeolite, carbon fiber powder and additive, and described additive is acid solution, water and binding agent, it is characterized in that by following composition quality proportional arrangement:
100 parts in zeolite
5～10 parts of carbon fiber powders
0.8～3 part of acid solution
1～6 part of binding agent
10～26 parts in water.
2. described a kind of complex sintered type zeolite adsorption formula refrigerating absorbent according to claim 1 is characterized in that described zeolite is 13X type molecular sieve, particle diameter 1～1.6mm; Described carbon fiber powder is high heat-conducting type, diameter 10 μ m, long 200 μ m.
3. described a kind of complex sintered type zeolite adsorption formula refrigerating absorbent according to claim 1 is characterized in that described acid solution is nitric acid, and the concentration of nitric acid is 1～10%.
4. described a kind of complex sintered type zeolite adsorption formula refrigerating absorbent according to claim 1, it is characterized in that, described binding agent is sodium carboxymethylcellulose and polyethylene glycol oxide, wherein the mass ratio of sodium carboxymethylcellulose and polyethylene glycol oxide is 1:0.4～4, and the mean molecule quantity of polyethylene glycol oxide is 300～4,000,000.
5. the preparation method of a complex sintered type zeolite adsorption formula refrigerating absorbent is characterized in that may further comprise the steps:
(1) in proportion zeolite, carbon fiber powder are dry mixed to get solid powder;
(2) in described solid powder, add acid solution in proportion, mix; Then add in proportion binding agent and water, mix; Then mixture is imported mould, compaction moulding; Then utilize ultrasonic echography to eliminate space between the particle;
(3) after the final drying, high-temperature calcination forms by a firing.
6. the preparation method of described a kind of complex sintered type zeolite adsorption formula refrigerating absorbent according to claim 5 is characterized in that, described to be dry mixed the time be 20～30min, and described mould is cylindric or square casing; Described ultrasonic time is 20～30min; The final temperature of described drying is 55 ~ 65 ℃; The final temperature of described calcining is 430～500 ℃, and 80 ℃/h of calcining heating rate keeps 4 h after the arrival maximum temperature.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140120A (en) * | 2016-07-13 | 2016-11-23 | 中国科学院广州能源研究所 | A method for solidifying adsorbent to enhance mass transfer |
| CN113967401A (en) * | 2015-07-09 | 2022-01-25 | 英格维蒂南卡罗来纳有限责任公司 | Gas storage system and methods of making and using the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113967401A (en) * | 2015-07-09 | 2022-01-25 | 英格维蒂南卡罗来纳有限责任公司 | Gas storage system and methods of making and using the same |
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Application publication date: 20130403 |