CN104986994A - Preparation method of blocky zirconium-carbon composite aerogel material - Google Patents
Preparation method of blocky zirconium-carbon composite aerogel material Download PDFInfo
- Publication number
- CN104986994A CN104986994A CN201510329666.6A CN201510329666A CN104986994A CN 104986994 A CN104986994 A CN 104986994A CN 201510329666 A CN201510329666 A CN 201510329666A CN 104986994 A CN104986994 A CN 104986994A
- Authority
- CN
- China
- Prior art keywords
- zirconium
- preparation
- zro
- mol ratio
- gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004964 aerogel Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 16
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 60
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000499 gel Substances 0.000 claims abstract description 22
- 238000000352 supercritical drying Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011240 wet gel Substances 0.000 claims abstract description 20
- 230000032683 aging Effects 0.000 claims abstract description 19
- 150000003754 zirconium Chemical class 0.000 claims abstract description 17
- 238000006073 displacement reaction Methods 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 24
- -1 polyoxyethylene Polymers 0.000 claims description 22
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 claims description 19
- 230000036571 hydration Effects 0.000 claims description 19
- 238000006703 hydration reaction Methods 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 238000007669 thermal treatment Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000004966 Carbon aerogel Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- PIYVNGWKHNMMAU-UHFFFAOYSA-N [O].O Chemical compound [O].O PIYVNGWKHNMMAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- QPZXVCVXJPXFPS-UHFFFAOYSA-N O(Cl)Cl.[Zr].[Zr] Chemical compound O(Cl)Cl.[Zr].[Zr] QPZXVCVXJPXFPS-UHFFFAOYSA-N 0.000 abstract 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000009413 insulation Methods 0.000 abstract 1
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 description 8
- 229950009789 cetomacrogol 1000 Drugs 0.000 description 8
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 8
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 6
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007783 nanoporous material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
Abstract
The invention belongs to the field of preparation processes of nanometer porous materials, and relates to a preparation method of a blocky zirconium-carbon composite aerogel material. With resorcinol and formaldehyde as the carbon source, inorganic zirconium salt zirconium oxychloride as a zirconium source, deionized water as a hydrolytic agent, alcohols as solvent and epoxide as a gel accelerator, under the effect of a basic catalyst, wet gel is prepared through sol-gel reaction, and the blocky high-temperature-resistant zirconium-carbon composite aerogel material is obtained after ageing, solvent displacement, supercritical drying and high-heat treatment are conducted on the wet gel. The material prepared with the cheap inorganic zirconium salt as the raw material is low in density, large in specific surface area, high in strength, resistant to high temperature and complete in structure, and the system has good prospects on the aspect of high-temperature thermal insulation and the aspect of serving as catalytic carriers.
Description
Technical field
The invention belongs to the preparation technology field of nano-porous materials, relate to the preparation method of a kind of carbon-zirconium compound airsetting hot material.Especially a kind of CO is used
2supercritical methanol technology prepares the preparation method of block zirconium-carbon aerogel composite.
Background technology
Aerogel is the nano-porous materials that a kind of nano particle is assembled mutually, and tool high-ratio surface sum porosity, therefore in calorifics, acoustics, optics etc., being all different from common solid-state material, is a kind of light nanoporous material with extensive use.The high porosity that aerogel material possesses can reduce solid thermal conduction, nano-porous structure can suppress air heat to conduct, the infrared light screening agent introduced can reduce radiative transfer, and this makes aerogel have excellent heat-proof quality, is the solid material of generally acknowledging that thermal conductivity is minimum at present.At present domestic and international to carbon-silicon, carbon-aluminium architectural study many, the research of carbon-zirconium system composite aerogel is not also specifically reported.The preparation of therefore block carbon-zirconium system aerogel has far-reaching influence for the optimization performance of material and the application of reinforcement material.
Summary of the invention
The object of the invention is the preparation method providing a kind of block zirconium-carbon aerogel composite in order to improve the deficiencies in the prior art, simply, with low cost, this material can be used for high temperature insulating for the method materials and technique, and as catalytic carrier.
Technical scheme of the present invention is: a kind of preparation method of block zirconium-carbon aerogel composite, and its concrete steps are as follows:
(1) inorganic zirconium salts being dissolved in solvent configuration, to obtain concentration be 0.1mol/L ~ 0.5mol/L inorganic zirconium salts solution, then in solution, add polyoxyethylene glycol and methane amide stirs, and obtains ZrO
2colloidal sol; Wherein the mol ratio of polyoxyethylene glycol and inorganic zirconium salts is (0.2 ~ 1): 1, and the mol ratio of methane amide and inorganic zirconium salts is (0.2 ~ 1): 1; Simultaneously by Resorcinol, formaldehyde, water, basic catalyst, according to formaldehyde: water: the mol ratio of Resorcinol is 2:(33 ~ 55): 1, Resorcinol: the mol ratio of basic catalyst is the ratio mixing of 80 ~ 120, stirs and obtains RF organosol;
(2) ZrO will obtained in step (1)
2colloidal sol and RF organosol are 1:(1 ~ 4 according to inorganic zirconium salts with the mol ratio of Resorcinol) mix, add propylene oxide after stirring, then stir to be placed in mould and treat its gel, obtain ZrO
2/ RF gel;
(3) then add Ageing solution to gel in mould in step (2), and the baking oven putting into 40 ~ 70 DEG C carries out burin-in process and replaces foreign ion;
(4) ZrO will obtained after burin-in process in step (3)
2/ RF compound wet gel carries out supercritical drying process, obtains block ZrO
2/ RF composite aerogel;
(5) ZrO will obtained in step (4)
2the thermal treatment under atmosphere protection of/RF composite aerogel, obtains block high temperature resistant carbon-zirconium aerogel material.
Solvent described in preferred steps (1) is water and ethanol is 1:(3 ~ 5 according to volume ratio) mixed solvent that configures.
Inorganic zirconium salts described in preferred steps (1) is one in eight hydration zirconium oxychlorides or six nitric hydrate oxygen zirconiums or its mixture.
Basic catalyst in preferred steps (1) is the one in anhydrous sodium carbonate, sodium hydroxide, calcium hydroxide or salt of wormwood.
The add-on of preferred steps (2) propylene oxide is the mol ratio of gate ring Ethylene Oxide and inorganic zirconium salts is (1 ~ 4): 1.
Ageing solution described in preferred steps (3) is one in ethanol, normal hexane or tetraethyl orthosilicate or its mixture; Burin-in process the displacement number of times of replacing foreign ion is 5 ~ 10 times, each time swap is 12 ~ 24h.
Supercritical drying described in preferred steps (4) is CO
2supercritical drying, with CO
2as drying medium, temperature of reaction is 45 ~ 60 DEG C, and in autoclave, pressure is 8 ~ 12MPa, and time of drying is 8 ~ 14h.
Atmosphere described in preferred steps (5) is the one in nitrogen, argon gas or helium.
In preferred steps (5), thermal treatment temp is 800 DEG C ~ 1500 DEG C, and heat treatment time is 3 ~ 10h.
The apparent density of the aerogel material that preferred steps (5) is obtained is 0.15 ~ 0.6g/cm
3, specific surface area is at 330 ~ 500m
2/ g, pore size distribution is at 5 ~ 50nm.
Beneficial effect:
The inventive method and there is following features by the block high temperature resistant zirconium-carbon aerogel composite of the method:
(1) raw material is inexpensive, reduces costs.What in present method, zirconium source was selected is inorganic zirconium salts, abandoned the Organic Alcohol zirconium adopted in general preparation process, and the price of inorganic zirconium salts is low, greatly reduces production cost.
(2) density is low, and the high temperature resistant zirconium of bulk-carbon aerogel composite density prepared by this invention is 0.15 ~ 0.6g/cm
2, density is significantly less than conventional high temperature insulating material.
(3) bulk high temperature resistant zirconium-carbon aerogel composite that the method is obtained, in sol-gel process, carbon reactant and zirconium reactant are not independent reactions, the wet gel obtained neither the mixing of simply carbon and zirconium, but reaction makes the network structure of wet gel interweave mutually each other, more firmly.Therefore aerogel good moldability, intensity greatly, can have good purposes.
Accompanying drawing explanation
Fig. 1 is the photo in kind of shape high temperature resistant zirconium-carbon aerogel composite that embodiment 1 obtains;
Fig. 2 is the nitrogen adsorption desorption curve of carbon-zirconium composite aerogel that embodiment 1 obtains;
Fig. 3 is that the SEM of block carbon-zirconium composite aerogel prepared by embodiment 3 shines.
Embodiment
Example 1
Be that 1:2 configures ZrO respectively according to eight hydration zirconium oxychlorides and Resorcinol mol ratio
2colloidal sol and RF colloidal sol, eight hydration zirconium oxychlorides are dissolved in ethanol and water volume ratio is make its concentration be 0.5mol/L in the mixed solvent of 1:4, add cetomacrogol 1000, methane amide wherein, the mol ratio of cetomacrogol 1000 and methane amide and eight hydration zirconium oxychlorides is 0.5:1, mixing and stirring, obtains ZrO
2colloidal sol.Formaldehyde: water: Resorcinol=2:55:1, Resorcinol: the mol ratio Homogeneous phase mixing of sodium carbonate=100 also obtains organosol (RF colloidal sol) after fully stirring.Above-mentioned 2 kinds of colloidal sols mixing is stirred, adds with zirconium oxychloride mol ratio the propylene oxide of the amount being 1:1 then wherein, pour in mould after stirring 15min, about 6h gel.RF/ZrO is obtained by above-mentioned
2gel to be put under room temperature after 12h, adds ethanol as the foreign ion in Ageing solution displacement wet gel, is then put in the baking oven of 50 DEG C, replaces 8 times, each 24h.Again by the RF/ZrO after aging
2compound wet gel puts into high temperature and high pressure kettle, utilizes CO
2supercritical drying carries out drying to sample, wherein CO
2pressure-controlling is at 10MPa, and temperature controls at 50 DEG C, and the supercritical drying time is 9h, thus the block RF/ZrO of obtained good forming ability
2composite aerogel.Again by organic aerogel under the protection of argon gas at 1500 DEG C thermal treatment 3h obtain required block carbon-zirconium aerogel composite.The photo in kind of obtained shape high temperature resistant zirconium-carbon aerogel composite is as shown in Figure 1: can find out that this composite aerogel is complete block, surface flawless, and possess certain mechanical strength, and its nitrogen adsorption desorption curve as shown in Figure 2: can find out that this curve is typical IV type curve, show that material is typical mesoporous material, specific surface area is large, is conducive to using as a kind of high temperature resistant heat insulation material.Its density 0.41g/cm is found through characterizing
2, specific surface area is 420.1m
2/ g, pore size distribution is at 5 ~ 30nm.
Example 2
Be that 1:1 configures ZrO respectively according to eight hydration zirconium oxychlorides and Resorcinol mol ratio
2colloidal sol and RF colloidal sol, eight hydration zirconium oxychlorides are dissolved in ethanol and water volume ratio is make its concentration be 0.5mol/L in the mixed solvent of 1:3, add Polyethylene Glycol-600, methane amide wherein, the mol ratio of Polyethylene Glycol-600 and methane amide and eight hydration zirconium oxychlorides is 0.2:1, mixing and stirring, obtains ZrO
2colloidal sol.Formaldehyde: water: Resorcinol=2:55:1, Resorcinol: the mol ratio Homogeneous phase mixing of salt of wormwood=100 also obtains organosol (RF colloidal sol) after fully stirring.Above-mentioned 2 kinds of colloidal sols mixing is stirred, adds with zirconium oxychloride mol ratio the propylene oxide of the amount being 1:1 then wherein, pour in mould after stirring 10min, about 8h gel.RF/ZrO is obtained by above-mentioned
2gel to be put under room temperature after 12h, adds ethanol as the foreign ion in Ageing solution displacement wet gel, is then put in the baking oven of 40 DEG C, replaces 10 times, each 24h.Again by the RF/ZrO after aging
2compound wet gel puts into high temperature and high pressure kettle, utilizes CO
2supercritical drying carries out drying to sample, wherein CO
2pressure-controlling is at 8MPa, and temperature controls at 60 DEG C, and the supercritical drying time is 12h, thus the block RF/ZrO of obtained good forming ability
2composite aerogel.Again by organic aerogel under the protection of argon gas at 1500 DEG C thermal treatment 10h obtain required block carbon-zirconium aerogel composite.Obtained composite aerogel density 0.51g/cm
2, specific surface area is 338.4m
2/ g, pore size distribution is at 10 ~ 40nm.
Example 3
Be that 1:4 configures ZrO respectively according to eight hydration zirconium oxychlorides and Resorcinol mol ratio
2colloidal sol and RF colloidal sol, eight hydration zirconium oxychlorides are dissolved in ethanol and water volume ratio is make its concentration be 0.5mol/L in the mixed solvent of 1:5, add cetomacrogol 1000, methane amide wherein, the mol ratio of cetomacrogol 1000 and methane amide and eight hydration zirconium oxychlorides is 0.8:1, mixing and stirring, obtains ZrO
2colloidal sol.Formaldehyde: water: Resorcinol=2:55:1, Resorcinol: the mol ratio Homogeneous phase mixing of sodium carbonate=100 also obtains organosol (RF colloidal sol) after fully stirring.Above-mentioned 2 kinds of colloidal sols mixing is stirred, adds with zirconium oxychloride mol ratio the propylene oxide of the amount being 1:1 then wherein, pour in mould after stirring 15min, about 5h gel.RF/ZrO is obtained by above-mentioned
2gel to be put under room temperature after 12h, adds ethanol as the foreign ion in Ageing solution displacement wet gel, is then put in the baking oven of 70 DEG C, replaces 5 times, each 12h.Again by the RF/ZrO after aging
2compound wet gel puts into high temperature and high pressure kettle, utilizes CO
2supercritical drying carries out drying to sample, wherein CO
2pressure-controlling is at 12MPa, and temperature controls at 45 DEG C, and the supercritical drying time is 8h, thus the block RF/ZrO of obtained good forming ability
2composite aerogel.Again by organic aerogel under the protection of argon gas at 1500 DEG C thermal treatment 3h obtain required block carbon-zirconium aerogel composite.As shown in Figure 3, the block carbon as can be seen from the figure obtained-zirconium composite aerogel is porous network structure to the SEM figure of prepared carbon-zirconium aerogel composite, finds its density 0.24g/cm through characterizing
2, specific surface area is 429.0m
2/ g, pore size distribution is at 5 ~ 40nm.
Example 4
Be that 1:2 configures ZrO respectively according to zirconium oxychloride and Resorcinol mol ratio
2colloidal sol and RF colloidal sol, eight hydration zirconium oxychlorides are dissolved in ethanol and water volume ratio is make its concentration be 0.1mol/L in the mixed solvent of 1:4, add Polyethylene Glycol-600, methane amide wherein, the mol ratio of Polyethylene Glycol-600 and methane amide and eight hydration zirconium oxychlorides is 1:1, mixing and stirring, obtains ZrO
2colloidal sol.Formaldehyde: water: Resorcinol=2:55:1, Resorcinol: the mol ratio Homogeneous phase mixing of sodium carbonate=80 also obtains organosol (RF colloidal sol) after fully stirring.Above-mentioned 2 kinds of colloidal sols mixing is stirred, adds with zirconium oxychloride mol ratio the propylene oxide of the amount being 3:1 then wherein, pour in mould after stirring 10min, about 3h gel.RF/ZrO is obtained by above-mentioned
2gel to be put under room temperature after 12h, adds ethanol as the foreign ion in Ageing solution displacement wet gel, is then put in the baking oven of 50 DEG C, replaces 7 times, each 24h.Again by the RF/ZrO after aging
2compound wet gel puts into high temperature and high pressure kettle, utilizes CO
2supercritical drying carries out drying to sample, wherein CO
2pressure-controlling is at 10MPa, and temperature controls at 50 DEG C, and the supercritical drying time is 10h, thus the block RF/ZrO of obtained good forming ability
2composite aerogel.Again by organic aerogel under the protection of helium at 1500 DEG C thermal treatment 5h obtain required block carbon-zirconium aerogel composite.Obtained composite aerogel density 0.17g/cm
2, specific surface area is 490.1m
2/ g, pore size distribution is at 10 ~ 50nm.
Example 5
Be that 1:2 configures ZrO respectively according to six nitric hydrate oxygen zirconiums and Resorcinol mol ratio
2colloidal sol and RF colloidal sol, six nitric hydrate oxygen zirconiums are dissolved in ethanol and water volume ratio is make its concentration be 0.5mol/L in the mixed solvent of 1:4, add cetomacrogol 1000, methane amide wherein, the mol ratio of cetomacrogol 1000 and methane amide and six nitric hydrate oxygen zirconiums is 0.5:1, mixing and stirring, obtains ZrO
2colloidal sol.Formaldehyde: water: Resorcinol=2:33:1, Resorcinol: the mol ratio Homogeneous phase mixing of sodium carbonate=120 also obtains organosol (RF colloidal sol) after fully stirring.Above-mentioned 2 kinds of colloidal sols mixing is stirred, adds with zirconium oxychloride mol ratio the propylene oxide of the amount being 1:1 then wherein, pour in mould after stirring 10min, about 6h gel.RF/ZrO is obtained by above-mentioned
2gel to be put under room temperature after 12h, adds normal hexane as the foreign ion in Ageing solution displacement wet gel, is then put in the baking oven of 50 DEG C, replaces 8 times, each 24h.Again by the RF/ZrO after aging
2compound wet gel puts into high temperature and high pressure kettle, utilizes CO
2supercritical drying carries out drying to sample, wherein CO
2pressure-controlling is at 10MPa, and temperature controls at 50 DEG C, and the supercritical drying time is 14h, thus the block RF/ZrO of obtained good forming ability
2composite aerogel.Again by organic aerogel under the protection of nitrogen at 800 DEG C thermal treatment 3h obtain required block carbon-zirconium aerogel composite.Obtained composite aerogel density 0.58g/cm
2, specific surface area is 377.2m
2/ g, pore size distribution is at 5 ~ 20nm.
Example 6
Be that 1:2 configures ZrO respectively according to eight hydration zirconium oxychlorides and Resorcinol mol ratio
2colloidal sol and RF colloidal sol, eight hydration zirconium oxychlorides are dissolved in ethanol and water volume ratio is make its concentration be 0.3mol/L in the mixed solvent of 1:4, add Polyethylene Glycol-600, methane amide wherein, the mol ratio of Polyethylene Glycol-600 and methane amide and eight hydration zirconium oxychlorides is 0.5:1, mixing and stirring, obtains ZrO
2colloidal sol.Formaldehyde: water: Resorcinol=2:55:1, Resorcinol: the mol ratio Homogeneous phase mixing of sodium carbonate=100 also obtains organosol (RF colloidal sol) after fully stirring.Above-mentioned 2 kinds of colloidal sols mixing is stirred, adds with zirconium oxychloride mol ratio the propylene oxide of the amount being 2.5:1 then wherein, pour in mould after stirring 10min, about 3h gel.RF/ZrO is obtained by above-mentioned
2gel to be put under room temperature after 12h, adds ethanol as the foreign ion in Ageing solution displacement wet gel, is then put in the baking oven of 50 DEG C, replaces 10 times, each 24h.Again by the RF/ZrO after aging
2compound wet gel puts into high temperature and high pressure kettle, utilizes CO
2supercritical drying carries out drying to sample, wherein CO
2pressure-controlling is at 10MPa, and temperature controls at 50 DEG C, and the supercritical drying time is 11h, thus the block RF/ZrO of obtained good forming ability
2composite aerogel.Again by organic aerogel under the protection of argon gas at 1500 DEG C thermal treatment 3h obtain required block carbon-zirconium aerogel composite.Obtained composite aerogel density 0.26g/cm
2, specific surface area is 488.7m
2/ g, pore size distribution is at 5 ~ 40nm.
Example 7
Be that 1:1.5 configures ZrO respectively according to eight hydration zirconium oxychlorides and Resorcinol mol ratio
2colloidal sol and RF colloidal sol, eight hydration zirconium oxychlorides are dissolved in ethanol and water volume ratio is make its concentration be 0.5mol/L in the mixed solvent of 1:4, add cetomacrogol 1000, methane amide wherein, the mol ratio of cetomacrogol 1000 and methane amide and eight hydration zirconium oxychlorides is 0.5:1, mixing and stirring, obtains ZrO
2colloidal sol.Formaldehyde: water: Resorcinol=2:55:1, Resorcinol: the mol ratio Homogeneous phase mixing of sodium hydroxide=100 also obtains organosol (RF colloidal sol) after fully stirring.Above-mentioned 2 kinds of colloidal sols mixing is stirred, adds with zirconium oxychloride mol ratio the propylene oxide of the amount being 1:1 then wherein, pour in mould after stirring 12min, about 7h gel.RF/ZrO is obtained by above-mentioned
2gel to be put under room temperature after 12h, adds ethanol as the foreign ion in Ageing solution displacement wet gel, is then put in the baking oven of 50 DEG C, replaces 8 times, each 24h.Again by the RF/ZrO after aging
2compound wet gel puts into high temperature and high pressure kettle, utilizes CO
2supercritical drying carries out drying to sample, wherein CO
2pressure-controlling is at 12MPa, and temperature controls at 45 DEG C, and the supercritical drying time is 8h, thus the block RF/ZrO of obtained good forming ability
2composite aerogel.Again by organic aerogel under the protection of argon gas at 1500 DEG C thermal treatment 5h obtain required block carbon-zirconium aerogel composite.Obtained composite aerogel density 0.48g/cm
2, specific surface area is 338.8m
2/ g, pore size distribution is at 5 ~ 30nm.
Claims (10)
1. a preparation method for block zirconium-carbon aerogel composite, its concrete steps are as follows:
(1) inorganic zirconium salts being dissolved in solvent configuration, to obtain concentration be 0.1mol/L ~ 0.5mol/L inorganic zirconium salts solution, then in solution, add polyoxyethylene glycol and methane amide stirs, and obtains ZrO
2colloidal sol; Wherein the mol ratio of polyoxyethylene glycol and inorganic zirconium salts is (0.2 ~ 1): 1, and the mol ratio of methane amide and inorganic zirconium salts is (0.2 ~ 1): 1; Simultaneously by Resorcinol, formaldehyde, water, basic catalyst, according to formaldehyde: water: the mol ratio of Resorcinol is 2:(33 ~ 55): 1, Resorcinol: the mol ratio of basic catalyst is the ratio mixing of 80 ~ 120, stirs and obtains RF organosol;
(2) ZrO will obtained in step (1)
2colloidal sol and RF organosol are 1:(1 ~ 4 according to inorganic zirconium salts with the mol ratio of Resorcinol) mix, add propylene oxide after stirring, then stir to be placed in mould and treat its gel, obtain ZrO
2/ RF gel;
(3) then add Ageing solution to gel in mould in step (2), and the baking oven putting into 40 ~ 70 DEG C carries out burin-in process and replaces foreign ion;
(4) ZrO will obtained after burin-in process in step (3)
2/ RF compound wet gel carries out supercritical drying process, obtains block ZrO
2/ RF composite aerogel;
(5) ZrO will obtained in step (4)
2the thermal treatment under atmosphere protection of/RF composite aerogel, obtains block high temperature resistant carbon-zirconium aerogel material.
2. preparation method according to claim 1, is characterized in that the solvent described in step (1) be water and ethanol is 1:(3 ~ 5 according to volume ratio) mixed solvent that configures.
3. preparation method according to claim 1, is characterized in that the inorganic zirconium salts described in step (1) is one in eight hydration zirconium oxychlorides or six nitric hydrate oxygen zirconiums or its mixture.
4. preparation method according to claim 1, the basic catalyst that it is characterized in that in step (1) is the one in anhydrous sodium carbonate, sodium hydroxide, calcium hydroxide or salt of wormwood.
5. preparation method according to claim 1, it is characterized in that the add-on of step (2) propylene oxide be the mol ratio of gate ring Ethylene Oxide and inorganic zirconium salts for (1 ~ 4): 1.
6. preparation method according to claim 1, is characterized in that the Ageing solution described in step (3) is one in ethanol, normal hexane or tetraethyl orthosilicate or its mixture; Burin-in process the displacement number of times of replacing foreign ion is 5 ~ 10 times, each time swap is 12 ~ 24h.
7. preparation method according to claim 1, is characterized in that the supercritical drying described in step (4) is CO
2supercritical drying, with CO
2as drying medium, temperature of reaction is 45 ~ 60 DEG C, and in autoclave, pressure is 8 ~ 12MPa, and time of drying is 8 ~ 14h.
8. preparation method according to claim 1, is characterized in that the atmosphere described in step (5) is the one in nitrogen, argon gas or helium.
9. preparation method according to claim 1, it is characterized in that in step (5), thermal treatment temp is 800 DEG C ~ 1500 DEG C, heat treatment time is 3 ~ 10h.
10. preparation method according to claim 1, is characterized in that the apparent density of the aerogel material that step (5) is obtained is 0.15 ~ 0.6g/cm
3, specific surface area is at 330 ~ 500m
2/ g, pore size distribution is at 5 ~ 50nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510329666.6A CN104986994B (en) | 2015-06-15 | 2015-06-15 | A kind of preparation method of block zirconium carbon aerogel composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510329666.6A CN104986994B (en) | 2015-06-15 | 2015-06-15 | A kind of preparation method of block zirconium carbon aerogel composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104986994A true CN104986994A (en) | 2015-10-21 |
| CN104986994B CN104986994B (en) | 2017-04-05 |
Family
ID=54298919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510329666.6A Active CN104986994B (en) | 2015-06-15 | 2015-06-15 | A kind of preparation method of block zirconium carbon aerogel composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104986994B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967727A (en) * | 2016-05-10 | 2016-09-28 | 南京工业大学 | Preparation method of carbon/ zirconium/ aluminum composite aerogel material |
| CN106007775A (en) * | 2016-05-10 | 2016-10-12 | 南京工业大学 | Preparation method of carbon fiber felt enhancing carbon/zirconium composite aerogel thermal insulation material |
| CN106938934A (en) * | 2017-02-28 | 2017-07-11 | 中国科学院上海硅酸盐研究所 | A kind of ultra-temperature ceramic-based aerogel material and preparation method thereof |
| CN108439409A (en) * | 2018-04-18 | 2018-08-24 | 南京工业大学 | A kind of preparation method of bulk boron carbide aeroge |
| CN109020619A (en) * | 2018-09-19 | 2018-12-18 | 蚌埠星烁新材料科技有限公司 | A kind of corrosion-resistant waterproof material suitable for concrete |
| CN110818423A (en) * | 2019-11-04 | 2020-02-21 | 江苏一夫新材料产业技术研究院有限公司 | Zirconium carbide-boron carbide composite aerogel and preparation method thereof |
| CN111346678A (en) * | 2020-03-30 | 2020-06-30 | 安徽元琛环保科技股份有限公司 | Preparation method of denitration catalyst with aerogel as carrier and prepared catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100190639A1 (en) * | 2009-01-28 | 2010-07-29 | Worsley Marcus A | High surface area, electrically conductive nanocarbon-supported metal oxide |
| CN102302917A (en) * | 2011-07-18 | 2012-01-04 | 南京工业大学 | Preparation method of bulk C-Al2O3 composite aerogel |
| CN102343285A (en) * | 2011-07-18 | 2012-02-08 | 南京工业大学 | Preparation method of blocky silicon-carbon composite aerogel |
| CN103157410A (en) * | 2013-03-13 | 2013-06-19 | 中国科学院化学研究所 | Aerogel preparation method |
| WO2015016638A1 (en) * | 2013-08-01 | 2015-02-05 | 주식회사 엘지화학 | Method for producing carbon carrier-metal nanoparticle complex and carbon carrier-metal nanoparticle complex produced thereby |
-
2015
- 2015-06-15 CN CN201510329666.6A patent/CN104986994B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100190639A1 (en) * | 2009-01-28 | 2010-07-29 | Worsley Marcus A | High surface area, electrically conductive nanocarbon-supported metal oxide |
| CN102302917A (en) * | 2011-07-18 | 2012-01-04 | 南京工业大学 | Preparation method of bulk C-Al2O3 composite aerogel |
| CN102343285A (en) * | 2011-07-18 | 2012-02-08 | 南京工业大学 | Preparation method of blocky silicon-carbon composite aerogel |
| CN103157410A (en) * | 2013-03-13 | 2013-06-19 | 中国科学院化学研究所 | Aerogel preparation method |
| WO2015016638A1 (en) * | 2013-08-01 | 2015-02-05 | 주식회사 엘지화학 | Method for producing carbon carrier-metal nanoparticle complex and carbon carrier-metal nanoparticle complex produced thereby |
Non-Patent Citations (2)
| Title |
|---|
| 李晓雷等: "无机盐源ZrO2块体气凝胶的制备", 《宇航材料工艺》 * |
| 李轩科等: "二元炭质-二氧化锆气凝胶制备Zr(C,O)纳米粉体", 《硅酸盐学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967727A (en) * | 2016-05-10 | 2016-09-28 | 南京工业大学 | Preparation method of carbon/ zirconium/ aluminum composite aerogel material |
| CN106007775A (en) * | 2016-05-10 | 2016-10-12 | 南京工业大学 | Preparation method of carbon fiber felt enhancing carbon/zirconium composite aerogel thermal insulation material |
| CN106938934A (en) * | 2017-02-28 | 2017-07-11 | 中国科学院上海硅酸盐研究所 | A kind of ultra-temperature ceramic-based aerogel material and preparation method thereof |
| CN108439409A (en) * | 2018-04-18 | 2018-08-24 | 南京工业大学 | A kind of preparation method of bulk boron carbide aeroge |
| CN109020619A (en) * | 2018-09-19 | 2018-12-18 | 蚌埠星烁新材料科技有限公司 | A kind of corrosion-resistant waterproof material suitable for concrete |
| CN110818423A (en) * | 2019-11-04 | 2020-02-21 | 江苏一夫新材料产业技术研究院有限公司 | Zirconium carbide-boron carbide composite aerogel and preparation method thereof |
| CN111346678A (en) * | 2020-03-30 | 2020-06-30 | 安徽元琛环保科技股份有限公司 | Preparation method of denitration catalyst with aerogel as carrier and prepared catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104986994B (en) | 2017-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104986994A (en) | Preparation method of blocky zirconium-carbon composite aerogel material | |
| CN103086692B (en) | Preparation method of blocky SiO2-Y2O3 compound aerogel | |
| CN103706342B (en) | Amino hybrid SiO 2aerogel material and application thereof | |
| CN105967727A (en) | Preparation method of carbon/ zirconium/ aluminum composite aerogel material | |
| CN101372337B (en) | Method for preparing transparent silicon dioxide aerogel by co-precursor normal atmosphere drying | |
| CN103191718B (en) | Preparation method of low-cost honeycomb denitration catalyst | |
| CN102010179B (en) | Method for preparing fiber-containing silicon dioxide aerogel composite thermal insulation material | |
| CN102343285B (en) | Preparation method of blocky silicon-carbon composite aerogel | |
| CN102718205B (en) | Method for preparing three-dimensional hierarchical porous carbon | |
| CN102302917B (en) | Preparation method of bulk C-Al2O3 composite aerogel | |
| CN105712400B (en) | Method for preparing zirconia aerogel material | |
| CN106365142A (en) | Preparation method of high-specific-surface-area high-electric-conductivity graphene compound carbon aerogel based on chemical crosslinking | |
| CN107998996B (en) | Preparation method of silicon-aluminum composite aerogel powder | |
| CN104402397A (en) | Preparation method of high-temperature-resistant block-shaped SiO2-Al2O3 composite aerogel thermal insulation material | |
| CN106007775A (en) | Preparation method of carbon fiber felt enhancing carbon/zirconium composite aerogel thermal insulation material | |
| CN104014286B (en) | A kind of TiO2-SiO2The preparation method of composite aerogel | |
| CN107841764B (en) | A kind of carbon dioxide electroreduction cathode and preparation method thereof | |
| CN102716700B (en) | Preparation method for high-strength heat-resisting massive C-AlN compound aerogel | |
| CN106186035A (en) | A kind of block La2o3siO2the preparation method of composite aerogel | |
| CN103539193B (en) | Preparation method of cerium-praseodymium composite oxide nanoparticle and nanorod | |
| CN103157461A (en) | Nanometer photocatalyst bismuth tungstate and preparation method thereof | |
| CN102731060A (en) | Preparation method for carbon fiber felt reinforced C-Al2O3 composite aerogel | |
| CN102351506A (en) | Preparation method of block high temperature resistant silicon-charcoal composite aerogel material | |
| CN106145999A (en) | A kind of block La2o3al2o3the preparation method of composite aerogel | |
| CN106431491A (en) | Preparation method of massive high-specific-area mullite-silicon carbide composite aerogel material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |