CN103922296B - A kind of spherical boron nitride and application thereof - Google Patents
A kind of spherical boron nitride and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of spherical boron nitride and application thereof.With template, boric acid and urea are raw material, preparation spherical boron nitride.Comprise the following steps: clarify water-soluble to template, nitrogenous source and boron source to solution; Settled solution is loaded in hydrothermal reaction kettle and heats, prepare presoma; Presoma is calcined in air atmosphere; Under protective atmosphere, Pintsch process; Products therefrom, after soaking, repeatedly cleans with water and ethanol, obtains the spherical boron nitride of high surface area.The spherical boron nitride specific surface area of inventing synthesis is herein large, has the stronger ability being adsorbed with organic pollutants, and preparation technology is simple, and cheaper starting materials does not need special catalyzer and other additive, method environmental protection.
Description
Technical field
The present invention relates to high adsorption activity spherical boron nitride material, belong to inorganic non-metallic materials science.
Background technology
Boron nitride is as a kind of important ceramic; there is a series of excellent properties features such as good mechanical property, heat conductivility is high, stable chemical nature, resistance of oxidation are strong, and the boron nitride material with high-ratio surface there is potential using value in fields such as hydrogen storage material, support of the catalyst, environment protection.
At present, industrial boron nitride powder be all adopt simple raw material as boric acid and urea or trimeric cyanamide obtained by the pyrolytic reaction batch production of metallurgy type, these powder are all random coacervate usually, and in the form of sheets, specific surface area is very low for profile.But nonetheless, boron nitride powder still has a lot of purposes, as the manufacture of high-temperature crucible, isolator, releasing agent, lubricant etc.Current, the non-oxidized substance inorganic ceramic solid powder material (as porous silicon nitride, boron nitride, gan etc.) of numerous novel high-ratio surface, high porosity causes the concern of researchist, and these materials are being used as all there is good application prospect in support of the catalyst, sensor, adsorbent, mould material etc.Up to the present, although boron nitride material has obvious advantage in many application aspect, still do not have a kind of easy easy method to carry out high yield and prepare highly purified special type boron nitride prod.
Summary of the invention
For the problems referred to above, the invention provides a kind of raw materials cheap, the simple and environmental protection of preparation technology, has the spherical boron nitride compared with high absorption capacity to organic pollutant.
The technical solution used in the present invention is: a kind of spherical boron nitride, its preparation method comprises the steps:
1) by water-soluble under magnetic stirring to template, nitrogenous source and boron source, colourless transparent solution is obtained; Wherein,
Described template is glucose, MCM-15 molecular sieve or y-zeolite; Preferred template is glucose;
Described nitrogenous source is urea, trimeric cyanamide, biuret, ammonium chloride or ammonium nitrate; Preferably, nitrogenous source is urea;
Described boron source preferred boric acid;
Preferably, the mol ratio in template, nitrogenous source and boron source is 1.0-8.5:1:1.
2) colourless transparent solution is put into stainless steel cauldron, reactor is positioned in constant temperature oven, in 180 DEG C-220 DEG C, reaction 24-110h, Temperature fall, to room temperature, filters, and uses water and washing with alcohol successively, obtains solid A after drying;
3) solid A is placed in High Temperature Furnaces Heating Apparatus, in air atmosphere, is warming up to 450-900 DEG C with the temperature rise rate of per minute 1-6 DEG C, at 450-900 DEG C, is incubated 2-12 hour, obtain solid B;
4) solid B is placed in encloses container, under a shielding gas, is warming up to 900-1700 DEG C with the temperature rise rate of per minute 1-6 DEG C, at 900-1700 DEG C, is incubated 1-14 hour, obtain solid C; Described shielding gas is ammonia or nitrogen.Preferably, shielding gas is nitrogen.
5) by solid C, with aqueous hydrochloric acid dipping 1-48 hour, and ultrasonic, stirring, then filter, precipitation water and washing with alcohol, then dry 3-24 hour at 50-150 DEG C, obtains target product spherical boron nitride.
It is larger that spherical boron nitride prepared by the present invention has specific surface area, the feature that appearance size is controlled, and cheaper starting materials, simple to operate, temperature of reaction is lower, low for equipment requirements, reduce production cost, and the boron nitride powder specific surface area generally prepared is less than normal, and preparation process is complicated, temperature of reaction is higher, higher to equipment requirements, and production cost is relatively high.
Spherical boron nitride of the present invention has higher adsorptive power to organic pollutant.Its method is as follows: in containing the waste water of organic pollutant, add above-mentioned spherical boron nitride, and the concentration of adjustment organic pollutant is 5-15mg/L, pH is 6.5-7.5, leaves standstill.
Spherical boron nitride of the present invention also has and applies widely in storage hydrogen, support of the catalyst etc.
The invention has the beneficial effects as follows: the present invention is by the water heat transfer preparation feedback presoma under template contral; through the control of template; the boron nitride formed has spherical basic appearance; then the template in calcination method removal presoma is adopted; again under a shielding gas; Pintsch process, then through soaking, obtained spherical boron nitride.And spherical size can carry out different control according to template different amounts, its size range is about 0.2 μm of-1.5 μm of scope.Cheaper starting materials of the present invention, wide material sources, and technique is simple, can obtain spherical boron nitride in lesser temps situation.Prepared spherical boron nitride specific surface area is large, and high porosity, has high absorption capacity to organic pollutant, and can reuse, and is with a wide range of applications in water treatment, purification, clean energy field.The absorption of spherical boron nitride of the present invention to organic pollutant presents the quick adsorption that a kind of 10s internal adsorption rate can reach 88%, higher adsorptive power is had to organic dye, and can reuse, and be also with a wide range of applications in hydrogen storage material, support of the catalyst and water treatment.
Accompanying drawing explanation
Fig. 1 is the infrared spectra of spherical boron nitride prepared by embodiment 1.
Fig. 2 is the X-ray powder diffraction pattern of spherical boron nitride prepared by embodiment 1.
Fig. 3 is the scanning electron microscope of spherical boron nitride prepared by embodiment 1.
Fig. 4 is the nitrogen nitrogen adsorption-desorption isotherm of spherical boron nitride prepared by embodiment 1.
Fig. 5 be in embodiment 16 spherical boron nitride to the relation of the adsorption time of methylene blue with clearance.
Fig. 6 be in embodiment 16 spherical boron nitride to the infrared spectrum of the adsorption and desorption of methylene blue.
Fig. 7 is the absorption situation of the recycle 5 times of spherical boron nitride in embodiment 16.
Embodiment
Below in conjunction with specific examples, technical scheme of the present invention is described further.
Embodiment 1 spherical boron nitride
(1) preparation method
1) by glucose, urea and boric acid be 1:1:1 in molar ratio, lower soluble in water assisting of magnetic agitation, obtain colourless transparent solution;
2) colourless transparent solution is put into 100ml stainless steel hydrothermal reaction kettle, reactor is put into constant temperature oven, at 180 DEG C, be incubated 24h; Naturally be down to room temperature, product is filtered, use water and washing with alcohol successively repeatedly, dry, obtain brown solid;
3) brown solid is placed in High Temperature Furnaces Heating Apparatus, in air atmosphere, is warming up to 450 DEG C with the temperature rise rate of per minute 1 DEG C, and be incubated 2 hours at this temperature, obtain light yellow solid;
4) light yellow solid is placed in container, under nitrogen protection, is warming up to 900 DEG C with the temperature rise rate of per minute 1 DEG C, and be incubated 2 hours at this temperature, obtain white solid;
5) by white solid, 1 hour is flooded with the aqueous hydrochloric acid that volume ratio is 1:1, and ultrasonic, stirring, then filter, precipitation water and ethanol repeatedly wash; At 50 DEG C, be incubated 3 hours, obtaining product is spherical boron nitride.
(2) Product Validation
1) as shown in Figure 1, as seen from Figure 1, product is at 1384cm for the infrared spectra of the spherical boron nitride prepared
-1and 786cm
-1absorption peak is clearly had near wave number, wherein, 1384cm
-1the absorption peak of place's correspondence is produced by stretching vibration in the face of B-N key, 786cm
-1the absorption peak at place is then formed by the out-of-plane deformation vibration of B-N-B key, and these absorption peaks are all the charateristic avsorption bands of boron nitride.
2) X-ray powder diffraction pattern of the spherical boron nitride prepared as shown in Figure 2, in 2 θ=26.70 °, 43.8 °, 55.1 ° have (002), (101) of diffraction peak and boron nitride, (004) crystal indices corresponding.
3) as shown in Figure 3,4, the boron nitride prepared as seen from Figure 3 is for spherical uniformly, and its diameter is about between 0.2-0.8 μm, and due to the control of template, product is spherical substantially for the scanning electron microscope of the spherical boron nitride prepared and adsorption curve.The specific surface area being calculated known product by Fig. 4 reaches 176.78m
2/ g, is better than some boron nitride materials reported at present, as active porous boron nitride (50m
2/ g), boron nitride (168m
2/ g), nm-class boron nitride (26.8m
2/ g) etc., fine sorbent material and support of the catalyst use can be done.
Embodiment 2 spherical boron nitride
Preparation method is with embodiment 1, and difference is the mol ratio changing glucose, urea and boric acid, and result is as table 1.
Table 1
| Glucose: urea: boric acid | 2：1：1 | 4：1：1 | 6：1：1 | 8：1：1 | 8.5：1：1 |
| The pattern of spherical boron nitride | 0.2-0.8μm | 0.3-1.0μm | 0.4-1.3μm | 0.6-1.4μm | 0.6-1.5μm |
From table 1, spherical size can be controlled, with satisfied different demand by changing glucose amount.
Embodiment 3 spherical boron nitride
Preparation method is with embodiment 1, and difference is: by step 1) in urea change trimeric cyanamide, biuret, ammonium chloride or ammonium nitrate respectively into, result is as table 2.
Table 2
| Nitrogenous source | Trimeric cyanamide | Biuret | Ammonium chloride | Ammonium nitrate |
| The pattern of spherical boron nitride | 0.2-1.5μm | 0.6-1.5μm | 0.5-1.3μm | 0.6-1.2μm |
Embodiment 4 spherical boron nitride
Preparation method is with embodiment 1, and difference is: by step 1) in glucose change MCM-41 molecular sieve or y-zeolite respectively into, result is as table 3.
Table 3
| Template | MCM-41 molecular sieve | Y-zeolite |
| The pattern of spherical boron nitride | 0.4-0.9μm | (0.3)-(1.2)μm |
Embodiment 5 spherical boron nitride
Preparation method is with embodiment 1, and difference is: change step 2) in soaking time, result is as table 4.
Table 4
Embodiment 6 spherical boron nitride
Preparation method is with embodiment 1, and difference is step 4) in shielding gas have nitrogen to change ammonia into, result is as table 5.
Table 5
| Shielding gas | Ammonia |
| The pattern of spherical boron nitride | 0.5-1.7μm |
Embodiment 7 spherical boron nitride
Preparation method with embodiment 1, difference be change step 2) in temperature, result is as table 6.
Table 6
Embodiment 8 spherical boron nitride
Preparation method is with embodiment 1, and difference is: change step 3) in temperature, result is as table 7.
Table 7
Embodiment 9 spherical boron nitride
Preparation method is with embodiment 1, and difference is to change temperature rise rate, and result is as table 8.
Table 8
| Step 3 temperature rise rate | 2 | 3 | 4 | 5 | 6 |
| Step 4 temperature rise rate | 2 | 3 | 4 | 5 | 6 |
| The pattern of spherical boron nitride | 0.2-1.3μm | 0.2-1.5μm | 0.2-1.1μm | 0.2-1.2μm | 0.2-1.2μm |
Embodiment 10 spherical boron nitride
Preparation method with embodiment 1, difference be change step 3) soaking time, result is as table 9.
Table 9
Embodiment 11 spherical boron nitride
Preparation method is with embodiment 1, and difference is change 4) temperature, result is as table 10.
Table 10
Embodiment 12 spherical boron nitride
Preparation method with embodiment 1, difference be change step 4) soaking time, result is as table 11.
Table 11
Embodiment 13 spherical boron nitride
Preparation method with embodiment 1, difference be change step 5) in dipping time, result is as table 3.
Table 3
Embodiment 14 spherical boron nitride
Preparation method with embodiment 1, difference be change step 5) in bake out temperature, result is as table 13.
Table 13
| Bake out temperature (DEG C) | 60 | 80 | 100 | 130 | 150 |
| The pattern of spherical boron nitride | 0.2-1.5μm | 0.2-1.3μm | 0.2-1.3μm | 0.2-1.4μm | 0.2-1.4μm |
Embodiment 15 spherical boron nitride
Preparation method with embodiment 1, difference be change step 5) in drying time, result is as table 14.
Table 14
Embodiment 16 application experiment
1) method is as follows: spherical boron nitride prepared by embodiment 1 added in the solution containing organic pollutant methylene blue, regulator solution pH is neutral, in 20ml, 10mg/L containing the spherical boron nitride adding 2mg embodiment 1 in methylene blue solution and prepare, standing adsorption.
2) adsorption time on the impact of adsorption rate as shown in Figure 5, and as seen from Figure 5, when adsorption time is 10s, adsorption rate can reach 88.64%, and adsorption time reaches balance to 20min later substantially, and adsorption rate is about 94.8%.
3) spherical boron nitride to the infrared spectrum of the adsorption and desorption of methylene blue as Fig. 6.As shown in Figure 6, in the infrared spectra of the rear sample of absorption, comparatively speaking, there is the absorption peak of obvious methylene blue, and after elevated temperature desorption process, the characteristic peak of a remaining nitride boron.
4) spherical boron nitride is through absorption, and then calcination processing is adsorbed again, and the adsorpting data of 5 circulations as shown in Figure 7.Each time of equilibrium adsorption is 30min, and the boron nitride after absorption repeats to do sorbent material through simple high-temperature calcination process and uses, and as seen from Figure 7, after recycle 5 times, adsorption rate still can close to 90%, and repeatability better.
Claims (8)
1. a spherical boron nitride, is characterized in that preparation method comprises the steps:
1) by water-soluble under magnetic stirring to template, nitrogenous source and boron source, colourless transparent solution is obtained; Wherein, described template is glucose, MCM-15 molecular sieve or y-zeolite; Described nitrogenous source is urea, trimeric cyanamide, biuret, ammonium chloride or ammonium nitrate; Described boron source is boric acid; The mol ratio in template, nitrogenous source and boron source is 1.0-8.5:1:1;
2) colourless transparent solution is put into stainless steel cauldron, reactor is positioned in constant temperature oven, in 180 DEG C-220 DEG C, reaction 24-110h, Temperature fall, to room temperature, filters, and precipitation uses water and washing with alcohol successively, obtains solid A after drying;
3) solid A is placed in High Temperature Furnaces Heating Apparatus, in air atmosphere, is warming up to 450-900 DEG C with the temperature rise rate of per minute 1-6 DEG C, at 450-900 DEG C, is incubated 2-12 hour, obtain solid B;
4) solid B is placed in encloses container, under a shielding gas, is warming up to 900-1700 DEG C with the temperature rise rate of per minute 1-6 DEG C, at 900-1700 DEG C, is incubated 1-14 hour, obtain solid C;
5) by solid C, with aqueous hydrochloric acid dipping 1-24 hour, and ultrasonic, stirring, then filter, precipitation water and washing with alcohol, then dry 3-24 hour at 50-150 DEG C, obtains target product spherical boron nitride.
2. spherical boron nitride as claimed in claim 1, is characterized in that: described template is glucose.
3. spherical boron nitride as claimed in claim 1, is characterized in that: described nitrogenous source is urea.
4. spherical boron nitride as claimed in claim 1, is characterized in that: described shielding gas is ammonia or nitrogen.
5. spherical boron nitride as claimed in claim 4, is characterized in that: described shielding gas is nitrogen.
6. spherical boron nitride according to claim 1 is being adsorbed with the application in organic pollutants.
7. apply as claimed in claim 6, it is characterized in that method is as follows: in containing the waste water of organic pollutant, add spherical boron nitride according to claim 1, the concentration of adjustment organic pollutant is 5-15mg/L, pH is 6.5-7.5, standing adsorption.
8. the application of spherical boron nitride according to claim 1 in hydrogen storage material, support of the catalyst and water treatment.
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| CN104740629B (en) * | 2015-04-01 | 2017-03-01 | 福州大学 | A kind of nanometer adjuvant and preparation method thereof |
| CN105921133A (en) * | 2016-07-15 | 2016-09-07 | 江苏省海洋资源开发研究院 | Composite adsorption nano-material and preparation method thereof |
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| CN108441986B (en) * | 2018-03-07 | 2020-09-08 | 南方科技大学 | Macroporous boron nitride fiber and preparation method thereof |
| CN108516839B (en) * | 2018-07-03 | 2021-04-30 | 辽宁大学 | Preparation method and application of boron nitride foam |
| CN109265178A (en) * | 2018-09-10 | 2019-01-25 | 湖北第二师范学院 | A kind of preparation method of the porous boron nitride foamed material for Water warfare |
| CN109706550B (en) * | 2019-01-14 | 2021-03-23 | 中原工学院 | Method for preparing hexagonal boron nitride by using carbon nanofibers as template |
| CN110386593A (en) * | 2019-07-04 | 2019-10-29 | 北京科技大学 | The method that the induction of amorphous precursor body synthesizes spherical boron nitride (BN) nano-powder |
| CN112225186B (en) * | 2020-10-21 | 2023-07-21 | 江西联锴科技有限公司 | Preparation method of spherical boron nitride |
| CN112675803B (en) * | 2020-11-19 | 2023-03-24 | 江苏大学 | Preparation and use methods of three-dimensional boron nitride nanosheet foam |
| CN116689014A (en) * | 2023-07-18 | 2023-09-05 | 江苏大学 | Multistage Kong Peng carbon-nitrogen material and preparation method and application thereof |
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| JP2010180066A (en) * | 2009-02-03 | 2010-08-19 | National Institute For Materials Science | Boron nitride spherical nanoparticle and method of producing the same |
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| CN103072959A (en) * | 2013-02-01 | 2013-05-01 | 湖北工业大学 | Preparation method of porous boron nitride |
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| JP2010180066A (en) * | 2009-02-03 | 2010-08-19 | National Institute For Materials Science | Boron nitride spherical nanoparticle and method of producing the same |
| CN102515120A (en) * | 2011-12-05 | 2012-06-27 | 沈阳大学 | Preparation method of hollow hexagonal boron nitride microsphere |
| CN103072959A (en) * | 2013-02-01 | 2013-05-01 | 湖北工业大学 | Preparation method of porous boron nitride |
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