CN103072959A - Preparation method of porous boron nitride - Google Patents
Preparation method of porous boron nitride Download PDFInfo
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- CN103072959A CN103072959A CN2013100402876A CN201310040287A CN103072959A CN 103072959 A CN103072959 A CN 103072959A CN 2013100402876 A CN2013100402876 A CN 2013100402876A CN 201310040287 A CN201310040287 A CN 201310040287A CN 103072959 A CN103072959 A CN 103072959A
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Abstract
The invention discloses a preparation method of porous boron nitride, and belongs to the technical field of materials. The method comprises the steps of using analytically pure nitrogen compound, boron compound and surfactant solid powder as the raw material; adequately dissolving and mixing; heating by water bath under severe stirring to form a mixture of the boron compound and the nitrogen compound; dehydrating and drying to obtain a boron nitride fiber precursor; then, filling the precursor in a corundum burning boat and placing the boat in a vacuum tubular furnace for pyrolysis in a flowing nitrogen atmosphere at a certain temperature for a period of time; and heating and insulating the pyrolytic product in a muffle furnace at a certain temperature for thermal treatment for a period of time to remove possible free carbon, sulphur and the like. The specific surface of porous boron nitride fiber prepared by the invention can reach 314.38m<2>/g<-1> and the porous boron nitride fiber is suitable for being used as a catalyst carrier. As material source is convenient and low in cost, and the preparation process is simple, so that large scale production is potentially realized by the method.
Description
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Technical field
The present invention relates to a kind of method for preparing porous boron nitride, belong to field of inorganic nonmetallic material.
Background technology
Porous material can be widely used in the fields such as support of the catalyst, hydrogen storage material, chemical filtering purification.Porous oxide carrier commonly used is such as SiO
2, γ-Al
2O
3Though zeolite molecular sieves etc. can provide higher specific surface area, but its thermal conductance efficient very low (easily causing between carrier and the metal sintering occuring), has hydrophilic surface (causing that easily catalyst surface covers last layer from the water in the surrounding environment), chemically reactive strong (easily forming acid sites or alkaline point at catalyst surface), examples of such carriers is under some harsh reaction conditionss, such as High Temperature High Pressure, strong acid, when raw material impurity content is high, to cause catalyst activity and life-span greatly to be reduced, so the range of application of porous oxide carrier is subject to certain restrictions.
The porous boron nitride hydrophobic nature is strong, chemical stability is high, fusing point is high, density is low, heat conductance is good, electrical insulating property is good, and under high temperature and intense light irradiation condition, still has good oxidation-resistance, oxidation resistance temperature reaches more than 800 ℃, so it can be used as the high temperature catalyst solid support material.As everyone knows, the specific surface area of support of the catalyst is higher, more is conducive to the dispersion of active ingredient, thereby improves its catalytic activity, yet commercially available boron nitride all is block boron nitride, and specific surface only is 25m
2About/g, more much lower than the specific surface of general support of the catalyst.Therefore, the technology of preparing of exploration high-ratio surface porous boron nitride has great importance.
At present, domestic and foreign literature had been reported a variety of high-ratio surface porous boron nitride material preparation technology, and these technology mainly comprise following three classes: 1. hydro-thermal, solvent thermal synthesis method; 2. template; 3. organic precursor method pyrolysis method.Yet all there are some shortcomings in this several method: generally on the low side such as the product yield that hydro-thermal, solvent thermal synthesis method make, most raw materials are unstable and poisonous, and environmental pollution is larger; Most of work rests on the little autoclave level in tens milliliters in laboratory and mostly is technical study in addition, and basic research is less, and the research dynamics of through engineering approaches aspect is inadequate, so that many achievements in research are difficult in time be converted into industrial-scale production.Template can be met difficulty in the middle of the aftertreatment of product, and the composition of template is difficult to effectively be removed, and is difficult to avoid the vesicular structure of boron nitride destroyed in the process of separating template in addition.Maximum precursor that the organic precursor method pyrolysis method adopts is single constituent element precursor, mainly contain amino borane and polymkeric substance thereof, trichlorine boron azine and polymkeric substance thereof, boron azine and polymkeric substance three classes thereof, although this method can make the boron nitride of high yield, high purity, high-ratio surface, but the organic precursor that relates to is synthetic very complicated, and output is lower, and this has limited the application and development of this method greatly.Therefore, explore economical and practical being of great significance without template, technology of preparing tool nontoxic, pollution-free and that output is large.Commonly used to a kind of foam process in the technology of preparing of porous ceramics, this technique mainly refers to add organic or Inorganic chemical substance in ceramic composition, the treatment stage form the gas of volatilization, produce foam, form hole, make porous ceramics through super-dry and sintering.The characteristics of this technique are to be diffused into by the gas that whipping agent discharges to obtain vesicular structure in the ceramic suspension body, and suspensoid generally comprises ceramic powder, solvent, tensio-active agent etc.Foam suspension can be by mechanical foaming, inject air-flow, utilize the approach such as volatilization of low-melting solvent of gas that chemical reaction produces or pyrolysis to obtain.Foam process prepares the foaming system that porous ceramics selects and mainly contains pneumatogen, inorganic foaming agent, organic blowing agent and tensio-active agent four classes, wherein tensio-active agent is the most frequently used pore forming material, utilizes it to pass through mechanical stirring and can form more stable foam.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of preparation method of nontoxic, the pollution-free and porous boron nitride that output is large is provided.
The inventive method prepares the boron nitride presoma by the slip foaming, makes the presoma high temperature pyrolysis again in flowing nitrogen atmosphere, forms hole and make the method for high-ratio surface porous boron nitride in the process of pyrolysis.
The technical scheme that the present invention addresses the above problem employing is:
(1) with nitrogen compound and the in molar ratio ratio weighing of 1:1～10 of boron compound, is configured to the mixed aqueous solution that total concn is 0.03～0.1g/ml; The tensio-active agent that in mixed aqueous solution, adds 1wt%～20wt%;
(2) the mixed aqueous solution vigorous stirring under 30～100 ℃ steady temperature that step (1) is made, stop after 1～10h stirring, place air naturally cooling 12～24h, after suction filtration, washing, vacuum-drying 16～24h, obtain the boron nitride fibre presoma;
(3) the boron nitride fibre presoma that step (2) is made places in the vacuum tube furnace, calcines 0.5～8h in 1300 ℃～1900 ℃ nitrogen atmospheres, subsequently naturally cooling;
(4) the high temperature pyrolysis product that step (3) is obtained places in the retort furnace, calcines 1～5h in 450 ℃～700 ℃ air, obtains final product.
In the step (3), nitrogen flow is 50～400ml/min.
Described nitride is trimeric cyanamide;
Described boride is boric acid;
Described tensio-active agent is Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or sodium lauryl sulphate.
X-ray diffraction pattern such as Fig. 1 of the nitride porous boron fibre that the inventive method obtains, each diffraction peak and hexagonal boron nitride match among the figure, and lattice parameter is a=2.462, c=6.740.The pattern of nitride porous boron fibre such as Fig. 2, Fig. 3.The isothermal adsorption of nitride porous boron fibre/desorption curve and pore size distribution such as Fig. 4, Fig. 5, the specific surface area of nitride porous boron fibre is 314.38m
2g
-1, even aperture distribution mainly concentrates on about 5.80nm.
The advantage of the inventive method is:
(1) specific surface of the nitride porous boron fibre of preparation can reach 314.38 m
2g
-1, be 13 times of block boron nitride, even aperture distribution mainly concentrates on about 5.80nm;
(2) cheap, the convenient sources and nontoxic of reaction raw materials is not used template in the reaction process, and is simple to operate, pollution-free, and the Residual reactants easy-clear is conducive to a large amount of productions.
Description of drawings
Fig. 1 is the x-ray diffraction pattern that the embodiment of the invention 1 makes product;
Fig. 2 is the SEM figure that the embodiment of the invention 1 makes product;
Fig. 3 is the TEM figure that the embodiment of the invention 1 makes product;
Fig. 4 is the embodiment of the invention 1 isothermal adsorption that makes product/desorption curve;
Fig. 5 is the graph of pore diameter distribution that the embodiment of the invention 1 makes product.
The implementation explanation
Further specify the present invention below by embodiment and embodiment.
In 300ml, 70 ℃ deionized water, add 10.07g trimeric cyanamide, 4.93g boric acid, be mixed with the mixing solutions that concentration is 0.05g/ml, then continue in mixing solutions, to add the 1.5g sodium lauryl sulphate, begin vigorous stirring and keep water temperature at 70 ℃ after adding, stop after the 4h stirring, place naturally cooling in room temperature, separate out white fiber shape crystal after the 20h.Obtain the precursor compound through suction filtration, washing, 105 ℃ of vacuum-drying 22h.The precursor compound corundum of packing into is burnt in the boat, place in the vacuum tube furnace, at flowing nitrogen atmosphere (purity nitrogen 99.88%, flow 200ml/min) carries out pyrolysis in 1580 ℃ of insulation 3h in, the product of pyrolysis is heat-treated in 550 ℃ of heat tracing 2h in retort furnace, to remove possible uncombined carbon, sulphur etc.Adopt full-automatic specific surface and lacunarity analysis instrument working sample specific surface and pore structure, with the specific surface area of BET Equation for Calculating sample, with BJH method calculated pore and pore size distribution (desorption branch), the specific surface area that records sample is 314.38m
2g
-1
In 300ml, 80 ℃ deionized water, add 6.07g trimeric cyanamide, 8.93g boric acid, be mixed with the mixing solutions that concentration is 0.05g/ml, then continue in mixing solutions, to add the 1.5g sodium lauryl sulphate, begin vigorous stirring and keep water temperature at 80 ℃ after adding, stop after the 6h stirring, place naturally cooling in room temperature, separate out white fiber shape crystal after the 20h.Obtain the precursor compound through suction filtration, washing, 110 ℃ of vacuum-drying 22h.The precursor corundum of packing into is burnt in the boat, place in the vacuum tube furnace, at flowing nitrogen atmosphere (purity nitrogen 99.88%, flow 300ml/min) carries out pyrolysis in 1550 ℃ of insulation 4h in, the product of pyrolysis is heat-treated in 550 ℃ of heat tracing 3h in retort furnace, to remove possible uncombined carbon, sulphur etc.Adopt full-automatic specific surface and lacunarity analysis instrument working sample specific surface and pore structure, with the specific surface area of BET Equation for Calculating sample, with BJH method calculated pore and pore size distribution (desorption branch), the specific surface area that records sample is 289m
2g
-1
Embodiment 3
In 300ml, 70 ℃ deionized water, add 7.57g trimeric cyanamide, 7.43g boric acid, be mixed with the mixing solutions that concentration is 0.05g/ml, then continue in mixing solutions, to add the 1.5g sodium lauryl sulphate, begin vigorous stirring and keep water temperature at 70 ℃ after adding, stop after the 4h stirring, place naturally cooling in room temperature, separate out white fiber shape crystal after the 18h.Obtain the precursor compound through suction filtration, washing, 100 ℃ of vacuum-drying 24h.The precursor corundum of packing into is burnt in the boat, place in the vacuum tube furnace, at flowing nitrogen atmosphere (purity nitrogen 99.88%, flow 250ml/min) carries out pyrolysis in 1580 ℃ of insulation 3h in, the product of pyrolysis is heat-treated in 550 ℃ of heat tracing 3h in retort furnace, to remove possible uncombined carbon, sulphur etc.Adopt full-automatic specific surface and lacunarity analysis instrument working sample specific surface and pore structure, with the specific surface area of BET Equation for Calculating sample, with BJH method calculated pore and pore size distribution (desorption branch), the specific surface area that records sample is 286m
2g
-1
Embodiment 4
In 300ml, 80 ℃ deionized water, add 7.57g trimeric cyanamide, 7.43g boric acid, be mixed with the mixing solutions that concentration is 0.05g/ml, then continue in mixing solutions, to add the 1.5g sodium laurylsulfonate, begin vigorous stirring and keep water temperature at 80 ℃ after adding, stop after the 4h stirring, place naturally cooling in room temperature, separate out white fiber shape crystal after the 18h.Obtain the precursor compound through suction filtration, washing, 100 ℃ of vacuum-drying 23h.The precursor corundum of packing into is burnt in the boat, place in the vacuum tube furnace, at flowing nitrogen atmosphere (purity nitrogen 99.88%, flow 150ml/min) carries out pyrolysis in 1500 ℃ of insulation 3h in, the product of pyrolysis is heat-treated in 550 ℃ of heat tracing 3h in retort furnace, to remove possible uncombined carbon, sulphur etc.Adopt full-automatic specific surface and lacunarity analysis instrument working sample specific surface and pore structure, with the specific surface area of BET Equation for Calculating sample, with BJH method calculated pore and pore size distribution (desorption branch), the specific surface area that records sample is 246m
2g
-1
Embodiment 5
In 300ml, 70 ℃ deionized water, add 7.57g trimeric cyanamide, 7.43g boric acid, be mixed with the mixing solutions that concentration is 0.05g/ml, then continue in mixing solutions, to add the 2.25g sodium lauryl sulphate, begin vigorous stirring and keep water temperature at 70 ℃ after adding, stop after the 3h stirring, place naturally cooling in room temperature, separate out white fiber shape crystal after the 20h.Obtain the precursor compound through suction filtration, washing, 95 ℃ of vacuum-drying 24h.The precursor compound corundum of packing into is burnt in the boat, place in the vacuum tube furnace, at flowing nitrogen atmosphere (purity nitrogen 99.88%, flow 100ml/min) carries out pyrolysis in 1500 ℃ of insulation 3h in, the product of pyrolysis is heat-treated in 600 ℃ of heat tracing 3h in retort furnace, to remove possible uncombined carbon, sulphur etc.Adopt full-automatic specific surface and lacunarity analysis instrument working sample specific surface and pore structure, with the specific surface area of BET Equation for Calculating sample, with BJH method calculated pore and pore size distribution (desorption branch), the specific surface area that records sample is 266.53m
2g
-1
Claims (5)
1. the preparation method of a porous boron nitride is characterized in that, comprises the steps:
(1) with nitrogen compound and the in molar ratio ratio weighing of 1:1～10 of boron compound, is configured to the mixed aqueous solution that total concn is 0.03～0.1g/ml; The tensio-active agent that in mixed aqueous solution, adds 1wt%～20wt%;
(2) the mixed aqueous solution vigorous stirring under 30～100 ℃ steady temperature that step (1) is made, stop after 1～10h stirring, place air naturally cooling 12～24h, after suction filtration, washing, vacuum-drying 16～24h, obtain the boron nitride fibre presoma;
(3) the boron nitride fibre presoma that step (2) is made places in the vacuum tube furnace, calcines 0.5～8h in 1300 ℃～1900 ℃ nitrogen atmospheres, subsequently naturally cooling;
(4) the high temperature pyrolysis product that step (3) is obtained places in the retort furnace, calcines 1～5h in 450 ℃～700 ℃ air, obtains final product.
2. preparation method as claimed in claim 1 is characterized in that, the described nitride of step (1) is trimeric cyanamide.
3. preparation method as claimed in claim 1 or 2 is characterized in that, the described boride of step (1) is boric acid.
4. preparation method as claimed in claim 1 or 2 is characterized in that, the described tensio-active agent of step (1) is Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or sodium lauryl sulphate.
5. preparation method as claimed in claim 1 or 2 is characterized in that, in the step (3), nitrogen flow is 50～400ml/min.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342570A (en) * | 2013-07-11 | 2013-10-09 | 山东宝纳新材料有限公司 | Method for preparing C/SiC composite material through low-cost fused silicon impregnation method |
| CN103922296A (en) * | 2014-04-30 | 2014-07-16 | 辽宁大学 | Spherical boron nitride and application thereof |
| CN104386657A (en) * | 2014-11-12 | 2015-03-04 | 河北工业大学 | Preparation method of high-crystallinity boron nitride |
| CN104499042A (en) * | 2014-12-15 | 2015-04-08 | 江苏苏博瑞光电设备科技有限公司 | Growth method of microporous sapphire crystal |
| CN105854919A (en) * | 2016-04-11 | 2016-08-17 | 广东工业大学 | Alpha-beta-unsaturated aldehyde low temperature hydrogenation catalyst, and preparation method and application thereof |
| CN106629636A (en) * | 2017-01-13 | 2017-05-10 | 河北工业大学 | Method for synthesizing porous boron nitride at low temperature with assistance of sulfonate |
| CN108178657A (en) * | 2018-01-12 | 2018-06-19 | 上海均博复合材料科技有限公司 | A kind of high intensity wave transparent ceramic shield and preparation method thereof |
| CN108516839A (en) * | 2018-07-03 | 2018-09-11 | 辽宁大学 | A kind of preparation method and application of boron nitride foam |
| CN109706549A (en) * | 2018-12-28 | 2019-05-03 | 沈阳航空航天大学 | A kind of preparation method and application of NEW TYPE OF COMPOSITE boron nitride adsorbent material |
| CN110573453A (en) * | 2017-03-17 | 2019-12-13 | Ip2Ipo创新有限公司 | Porous boron nitride |
| CN112877810A (en) * | 2021-02-01 | 2021-06-01 | 山东大学 | Preparation method of porous boron nitride fiber with high specific surface area |
| CN114855453A (en) * | 2022-06-17 | 2022-08-05 | 西安理工大学 | Preparation method of high-thermal-conductivity composite material with self-assembled fiber-like monolithic structure |
| CN115477309A (en) * | 2022-09-01 | 2022-12-16 | 中国人民解放军国防科技大学 | High-ceramic-yield carbon-free boron nitride precursor anti-aqueous-oxygen modification method |
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Cited By (20)
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| CN103342570A (en) * | 2013-07-11 | 2013-10-09 | 山东宝纳新材料有限公司 | Method for preparing C/SiC composite material through low-cost fused silicon impregnation method |
| CN103342570B (en) * | 2013-07-11 | 2014-08-20 | 山东宝纳新材料有限公司 | Method for preparing C/SiC composite material through low-cost fused silicon impregnation method |
| CN103922296A (en) * | 2014-04-30 | 2014-07-16 | 辽宁大学 | Spherical boron nitride and application thereof |
| CN103922296B (en) * | 2014-04-30 | 2015-10-28 | 辽宁大学 | A kind of spherical boron nitride and application thereof |
| CN104386657A (en) * | 2014-11-12 | 2015-03-04 | 河北工业大学 | Preparation method of high-crystallinity boron nitride |
| CN104499042A (en) * | 2014-12-15 | 2015-04-08 | 江苏苏博瑞光电设备科技有限公司 | Growth method of microporous sapphire crystal |
| CN105854919A (en) * | 2016-04-11 | 2016-08-17 | 广东工业大学 | Alpha-beta-unsaturated aldehyde low temperature hydrogenation catalyst, and preparation method and application thereof |
| CN106629636A (en) * | 2017-01-13 | 2017-05-10 | 河北工业大学 | Method for synthesizing porous boron nitride at low temperature with assistance of sulfonate |
| CN110573453B (en) * | 2017-03-17 | 2023-04-11 | 帝国理工学院创新有限公司 | Porous boron nitride |
| CN110573453A (en) * | 2017-03-17 | 2019-12-13 | Ip2Ipo创新有限公司 | Porous boron nitride |
| CN108178657A (en) * | 2018-01-12 | 2018-06-19 | 上海均博复合材料科技有限公司 | A kind of high intensity wave transparent ceramic shield and preparation method thereof |
| CN108178657B (en) * | 2018-01-12 | 2021-02-02 | 上海均博复合材料科技有限公司 | High-strength wave-transparent ceramic cover and preparation method thereof |
| CN108516839A (en) * | 2018-07-03 | 2018-09-11 | 辽宁大学 | A kind of preparation method and application of boron nitride foam |
| CN108516839B (en) * | 2018-07-03 | 2021-04-30 | 辽宁大学 | Preparation method and application of boron nitride foam |
| CN109706549A (en) * | 2018-12-28 | 2019-05-03 | 沈阳航空航天大学 | A kind of preparation method and application of NEW TYPE OF COMPOSITE boron nitride adsorbent material |
| CN109706549B (en) * | 2018-12-28 | 2021-07-13 | 沈阳航空航天大学 | Preparation method and application of novel composite boron nitride adsorption material |
| CN112877810A (en) * | 2021-02-01 | 2021-06-01 | 山东大学 | Preparation method of porous boron nitride fiber with high specific surface area |
| CN114855453A (en) * | 2022-06-17 | 2022-08-05 | 西安理工大学 | Preparation method of high-thermal-conductivity composite material with self-assembled fiber-like monolithic structure |
| CN114855453B (en) * | 2022-06-17 | 2024-03-08 | 西安理工大学 | Preparation method of self-assembled fiber-imitated monolithic structure high-heat-conductivity composite material |
| CN115477309A (en) * | 2022-09-01 | 2022-12-16 | 中国人民解放军国防科技大学 | High-ceramic-yield carbon-free boron nitride precursor anti-aqueous-oxygen modification method |
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Application publication date: 20130501 |