CN1166450C - Preparation and use of nano porous silica gel adsorbent material - Google Patents
Preparation and use of nano porous silica gel adsorbent material Download PDFInfo
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- CN1166450C CN1166450C CNB021497176A CN02149717A CN1166450C CN 1166450 C CN1166450 C CN 1166450C CN B021497176 A CNB021497176 A CN B021497176A CN 02149717 A CN02149717 A CN 02149717A CN 1166450 C CN1166450 C CN 1166450C
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Abstract
The present invention provides a preparation method of nano porous silica gel adsorbent material, which comprises the following steps: (1), at room temperature, inorganic fiber paper is immersed in water glass; after 10 to 24 hours, the inorganic fiber paper is taken out and dried for 10 to 24 hours; (2), a precipitating agent is prepared into water solution for immersing the inorganic fiber paper to sufficiently react for 12 to 24 hours; (3), the inorganic fiber paper after a reaction is aired and immersed for 12 to 24 hours with acid solution; then, the inorganic fiber paper is washed with water until the pH is neutral; the inorganic fiber paper is taken out and aired; temperature programming treatment is adopted for obtaining nano porous silica gel adsorbent material. A nano porous silica gel adsorbent prepared by the method can be used for preparing adsorption gas dehumidification dryness or dehumidification rotary cores in adsorption air conditioners. The present invention has the advantages of large adsorption quantity, little energy consumption, low regeneration temperature, energy saving, material saving and wide application prospect.
Description
Technical field
The present invention relates to the absorption type gas purification technique, particularly a kind of nano aperture silica gel absorber preparation methods and application thereof.
Background technology
The absorption type gas purification technique significantly becomes one of technology of sustainable development in advantage aspect low-grade energy utilization and the environmental protection.In the absorption type gas purification technique, absorption working pair is the key of decision adsorption system performance, absorption working pair of having developed and combination thereof reach over one hundred kind, but select from the practicality of adsorbent, the adsorbent that is used for absorption type rotation dehumidifier at present only limits to the contour hygroscopic matter of lithium chloride, silica gel and molecular sieve; The lithium chloride good hygroscopicity, regeneration temperature is low, but peripheral hardware is had corrosivity; Molecular sieve is suitable for low dew point degree of depth dehumidifying, but regeneration temperature height (more than 250 ℃); The performance of silica gel is between between the two, not only be applicable to conventional dehumidifying (silochrom) but also be applicable to low dew point degree of depth dehumidifying (Kiselgel A), wherein Kiselgel A is applicable to that making the silica gel dehumidifying changes core, and the key of making silica gel dehumidifying commentaries on classics core is the combination of silica gel and inorfil base material; It can adopt adhesive with silica gel powder bonding making on the inorfil base material, but because a little less than powder and the base material interface interaction power, adhesion is relatively poor, under higher temperature, use repeatedly under (more than 150 ℃), be prone to the dry linting phenomenon, make silica gel change the core performance instability, simultaneously, base material and silica gel duct can be partly stopped up in the use of adhesive, and the silica gel specific area is descended, thereby adsorption efficiency is reduced; Also can on the inorfil base material, adopt conventional preparation of silica gel method allow waterglass and acid reaction, but owing to be subjected to the restriction of collosol stability to be difficult to form high concentration colloidal sol, inorfil is water insoluble in addition, contact-making surface is little between colloidal sol and fiber, thereby the colloidal sol amount of adhering on inorfil is few, the silica gel that generates is few,, dehumidification rate is low.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of superior performance is provided, adsorbance is big, the nano aperture silica gel absorber preparation methods that adsorption/desorption speed is fast, regeneration temperature is low.
Another object of the present invention is to provide of the application of a kind of above-mentioned nano aperture silica gel absorption agent material at dehumidify field.
Purpose of the present invention is achieved through the following technical solutions: this nano aperture silica gel absorber preparation methods comprises the steps:
(1) under the room temperature inorganic fibre paper is immersed in the waterglass, takes out after 10~24 hours, dry 10~24 hours;
(2) precipitating reagent is made into the aqueous solution and floods above-mentioned inorganic fibre paper, the silicate precipitates of generation is deposited in the surface and space thereof of inorfil, fully reacts 12~24 hours;
(3) reacted inorganic fibre paper is dried, again with acid solution dipping 12~24 hours, then water wash to pH for neutral, taking-up is dried, and adopts temperature programming to handle and obtains nano aperture silica gel absorption agent material.
Described modulus of water glass is 2.2~3.7, and concentration of sodium silicate is 10~50% (percentage by weights); Not stopping up the honeycomb duct when selection of modulus of water glass is changeed core with the dehumidifying of dipping honeycomb is prerequisite, and the selection of its concentration then mostly is condition as far as possible with base material kiss-coating amount, takes into account the intensity after base material floods simultaneously; General concentration of sodium silicate is high more, and the kiss-coating amount is many more, but the easy embrittlement of base material, be unfavorable for subsequent treatment, the inventor finds that by repetition test the modulus of waterglass is 2.8~3.7, the waterglass weight percent concentration is 20~35% o'clock, and silica obtained dehumidifying is changeed core and had maximal absorptive capacity.
Described precipitating reagent is a soluble calcium salt, as calcium chloride, and calcium nitrate etc., its concentration is 5%~40% (percentage by weight); The concentration of precipitating reagent is too low then to be unfavorable for deposition, too highly then deposits inhomogeneously, can part stops up and changes the core duct, the experiment proved that effect preferably matched proportion density be 20~35% (percentage by weights).
Described acid strength is 0.05~1.2mol/L; When selecting acid, must consider acid solution to changeing the corrosivity (as nitric acid) of core, except that generating the silica gel precipitation, can not form other sediment (as phosphoric acid) or micro-soluble material (as sulfuric acid) in the time of will considering acid with the calcium silicates reaction simultaneously, suitable acid is hydrochloric acid.It is condition that the selection of acid concentration then keeps suitable speed with hydrolysis, in-situ polymerization, concentration is too high, and hydrolysis, in-situ polymerization and gelation speed are too fast, and the silica gel product that is generated covers the surface of calcium silicates, form barrier layer, stop calcium silicates and further reaction of acid; Concentration is too low, and reaction rate is too slow, and it is long to change the core dip time; Its effect of empirical tests concentration preferably is 0.3~0.8mol/L.
It is slowly to heat up down at 200~300 ℃ earlier that temperature programming described in the step (3) is handled, and cooling naturally, 2~3 times repeatedly, slowly be warmed up to 500~550 ℃ again, and be incubated 1~3 hour, then cooling naturally; Taking temperature programming technology is for moisture and volatile impurity in removing the commentaries on classics core, and in the process that forms the Si-O-Si network, reduces the contraction rate of gel as much as possible, avoids the material internal regional stress to concentrate and crack, and reduces the fragility of material.
The present invention is by adding the method for precipitating reagent, make the precipitated calcium silicate of generation be deposited on the space and the surface of inorfil in a large number, add acid then and make the slow hydrolysis of calcium silicates on the inorfil, and in-situ polymerization, again through moulding, sintering processes, synthesize and have high adsorption capacity, the nano aperture sorbent material of low regeneration temperature; The dehumidifying that prepared nano aperture sorbent material can be applied in absorption type gas dehumidification drying or the absorption type refrigerating air-conditioning is changeed in the core apparatus.
The present invention has following advantage and effect with respect to prior art: (1) adsorbance is big, consuming little energy; Use the dehumidifying commentaries on classics core of this nano aperture sorbent material to have than the slow-speed of revolution, the energy requirement that core is changeed in corresponding rotation dehumidifying is low, transmission loss is little; (2) adsorption/desorption speed is fast; (3) regeneration temperature is low; Can save heat widely like this, consider from energy-conservation angle, available energy increases in the heat that thermal source provides, that is has improved and gush efficient; (4) energy-saving material-saving; The nano aperture silica gel absorption agent material that utilizes the present invention to prepare has higher hygroscopic capacity and lower operating temperature, can reduce equipment volume and cut down the consumption of energy, and reaches the purpose of energy-saving material-saving; The experiment proved that, utilize its performance of nano aperture silica gel absorption agent material of the inventive method preparation obviously to be better than product of the same type, this nano aperture silica gel absorption agent material can make dehumidifying change that core volume dwindles 20%~30%, energy consumption reduces by 25~35%, and the saving metal material and energy effect is remarkable.
Description of drawings
Fig. 1 is with the nano aperture silica gel absorber of the inventive method preparation isothermal adsorption curve when the 298K.
Fig. 2 is the isothermal adsorption curve figures of different adsorbents [silica gel (embodiment 1 preparation), Kiselgel A, 4A molecular sieve] when 298 K.
Fig. 3 is 298K, and under the 3.0KPa steam partial pressure, the adsorbance of silica gel absorber (embodiment 1 preparation) is schemed over time.
Fig. 4 is the comparison diagram of different adsorbent desorption abilities under the 13.0KPa steam partial pressure.
Fig. 5 is the graph of pore diameter distribution of the silica gel of embodiment 1 preparation.
The specific embodiment
The inventor has a lot of successful implementation examples through in a few years development.In order to illustrate that better the present invention had both increased moisture removal, improved absorption property, reduced regeneration temperature again, enlarged the scope of application of the renewable sources of energy, enumerate 3 embodiment of the present invention below, and in conjunction with the accompanying drawings its technical performance index is compared, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) under the room temperature, in 200L round plastic container, add 120L water, add modulus then and be 3.0 waterglass 40Kg, after stirring, the honeycomb of the moulding that inorganic fibre paper is made changes core, and ( 500mm * 200mm) puts into and wherein floods 12 hours, it is fully soaked into, taking-up is dried, and 60 ℃ of following low temperature dryings 18 hours, is cooled to room temperature then; (2) anhydrous calcium chloride that takes by weighing 25Kg is dissolved in the water of 125L, above-mentioned honeycomb is changeed core immerse wherein, reacts to take out after 12 hours and dries, and places baking oven in 60 ℃ of low temperature dryings 24 hours again, is cooled to room temperature; (3) the industrial concentrated hydrochloric acid of measuring 10L is diluted to 160L, above-mentioned honeycomb is changeed core to be immersed wherein, take out after 20 hours water wash to pH for neutral, dry the back in 40 ℃ of thermostatic drying chambers dry 24 hours, will change core then to be placed in the intelligent constant-temperature sintering furnace, slowly heat up down at 200~300 ℃ earlier, and cooling naturally, 2~3 times repeatedly, slowly be warmed up to 500~550 ℃ again, be incubated 1~3 hour, naturally cool to the dehumidifying commentaries on classics core that room temperature obtains containing the nano aperture silica gel absorber then.
Embodiment 2
(1) under the room temperature, in 200L round plastic container, add 100L water, add modulus then and be 3.0 waterglass 40Kg, after stirring, the honeycomb of the moulding that inorganic fibre paper is made changes core, and ( 500mm * 200mm) puts into and wherein floods 12 hours, it is fully soaked into, taking-up is dried, and 60 ℃ of following low temperature dryings 18 hours, is cooled to room temperature then; (2) take by weighing the 30Kg anhydrous calcium chloride and be dissolved in the water of 120L, above-mentioned honeycomb is changeed core immerse wherein, react to take out after 12 hours and dry, place baking oven again, be cooled to room temperature in 60 ℃ of low temperature dryings 24 hours; (3) the industrial concentrated hydrochloric acid of measuring 10L is diluted to 160L, above-mentioned honeycomb is changeed core to be immersed wherein, take out after 20 hours water wash to pH for neutral, dried in back 40 ℃ of thermostatic drying chambers dry 24 hours, will change core then to be placed in the intelligent constant-temperature sintering furnace, slowly heat up down at 200~300 ℃ earlier, and cooling naturally, 2~3 times repeatedly, slowly be warmed up to 500~550 ℃ again, be incubated 1~3 hour, naturally cool to the dehumidifying commentaries on classics core that room temperature obtains containing the nano aperture silica gel absorber then.
Embodiment 3
(1) under the room temperature, in 200L round plastic container, add 120L water, add modulus then and be 3.0 waterglass 30Kg, after stirring, the honeycomb of the moulding that inorganic fibre paper is made changes core, and ( 500mm * 200mm) puts into wherein to flood and it was fully soaked in 12 hours, and taking-up is dried, at 60 ℃ of following low temperature drying 18h, be cooled to room temperature then; (2) anhydrous calcium chloride that takes by weighing 20Kg is dissolved in the water of 140 L, above-mentioned honeycomb is changeed core immerse wherein, takes out after 12 hours and dries, and places baking oven in 60 ℃ of low temperature dryings 24 hours again, is cooled to room temperature; (3) the industrial concentrated hydrochloric acid of measuring 9L is diluted to 160L, above-mentioned honeycomb is changeed core to be immersed wherein, take out after 20 hours water wash to pH for neutral, dry the back in 40 ℃ of thermostatic drying chambers dry 24 hours, will change core then to be placed in the intelligent constant-temperature sintering furnace, slowly heat up down at 200~300 ℃ earlier, and cooling naturally, 2~3 times repeatedly, slowly be warmed up to 500~550 ℃ again, insulation 1-3h naturally cools to room temperature then and obtains containing nano aperture silica gel absorption agent material dehumidifying commentaries on classics core.
The prepared sorbent material of the foregoing description is carried out the test of isothermal characterization of adsorption.Fig. 1 as seen from Figure 1, adopts the silica gel absorber of this preparation method gained to have very high absorption property for by the isothermal adsorption curve of the silica obtained adsorbent of different proportionings when 298K, and to adopt the silica gel absorption better performances of example 1 gained, reaches 65.7%; Fig. 2 is different adsorbent isothermal adsorption curves, and as shown in Figure 2, the absorption property of the silica gel absorber of the present invention's preparation is significantly better than products such as (Kiselgel A) of the same type, molecular sieves; Figure 3 shows that the silica gel absorption amount over time, visible silica gel absorber had the very high rate of adsorption at preceding 15 minutes, and the rate of adsorption slows down thereafter; Fig. 4 is the comparison of different adsorbent desorption abilities, and as can be seen from Figure 4, the desorption ability and the Kiselgel A of silica gel absorber are suitable, but apparently higher than molecular sieve, this shows that silica gel absorber has lower regeneration temperature; Fig. 5 is the pore-size distribution of embodiment 1 silica obtained adsorbent, and test result shows that the silica gel absorber aperture overwhelming majority drops in the scope of 3~6nm, because the silica gel aperture is little, specific area is big, thereby water vapour is had huge adsorption capacity.
In sum, utilize prepared its performance parameter of nano aperture silica gel absorber of the inventive method obviously to be better than adsorbent of the same type, it is big to have adsorbance, adsorption/desorption speed is fast, advantages such as regeneration temperature is low, and the energy-saving material-saving effect is remarkable can be widely applied in the manufacturing of desiccant wheel.
Claims (6)
1, a kind of nano aperture silica gel absorber preparation methods, it is characterized in that comprising the steps: under (1) room temperature inorganic fibre paper is immersed in modulus and be 2.2~3.7, concentration is in the waterglass of 10~50% (percentage by weights), take out dry 10~24 hours after 10~24 hours; (2) be that 5%~40% soluble calcium salt is made into the aqueous solution and floods above-mentioned inorganic fibre paper with concentration, fully reacted 12~24 hours; (3) reacted inorganic fibre paper being dried, is the acid solution dipping 12~24 hours of 0.05~1.2mol/L again with concentration, then water wash to pH for neutral, taking-up is dried, and adopts temperature programming to handle and obtains nano aperture silica gel absorption agent material.
2, nano aperture silica gel absorber preparation methods according to claim 1 is characterized in that: the concentration of described soluble calcium salt is 20%~35% (percentage by weight).
3, nano aperture silica gel absorber preparation methods according to claim 1, it is characterized in that: described soluble calcium salt is calcium chloride or calcium nitrate.
4, nano aperture silica gel absorber preparation methods according to claim 1, it is characterized in that: the concentration of described acid solution is 0.3~0.8mol/L.
5, nano aperture silica gel absorber preparation methods according to claim 1, it is characterized in that: it is slowly to heat up down at 200~300 ℃ earlier that described temperature programming is handled, and cooling naturally, 2~3 times repeatedly, slowly be warmed up to 500~550 ℃ again, be incubated 1~3 hour, then cooling naturally.
6, a kind of application as the nano aperture silica gel absorption agent material of method preparation as described in each claim of claim 1~5 is characterized in that: core is changeed in the dehumidifying that is used for preparing absorption type gas dehumidification drying or absorption type refrigerating air-conditioning.
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CN100352540C (en) * | 2005-04-06 | 2007-12-05 | 华南理工大学 | Method for preparing titanium modified silica gel adsorption block |
TWI383951B (en) * | 2006-05-09 | 2013-02-01 | Mitsubishi Gas Chemical Co | Method for producing hydrogen peroxide containing a regeneration step of an action solution |
CN1986046B (en) * | 2006-11-27 | 2010-09-01 | 华南理工大学 | Preparing process of composite block adsorbent of molecular sieve and modified silica gel |
CN102847672A (en) * | 2012-09-26 | 2013-01-02 | 胡成岚 | Adsorbent bonding method applied to rotary dehumidifier |
CN104848470B (en) * | 2015-02-09 | 2018-03-13 | 钱鸿斌 | Nano material, its preparation method and apply its dehydrating unit, dehumanization method |
WO2017172038A2 (en) | 2016-02-02 | 2017-10-05 | University Of Washington | Ceramic selective membranes |
BR112020013645A2 (en) | 2018-01-04 | 2020-12-01 | University Of Washington | nanoporous selective sol-gel ceramic membrane, selective membrane structures and related methods |
CN111408337A (en) * | 2020-03-17 | 2020-07-14 | 江苏苏净集团有限公司 | Silica gel dehumidification rotating wheel and preparation method thereof |
CN117225539B (en) * | 2023-09-22 | 2024-04-05 | 硅宝石(武汉)高新装备股份有限公司 | Preparation method of large-aperture silica gel honeycomb dehumidifying material |
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