CN102806068B - Preparation method of carbon nanotube and molecular sieve composite for removing metal ions in ultra-pure ammonia - Google Patents
Preparation method of carbon nanotube and molecular sieve composite for removing metal ions in ultra-pure ammonia Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon nanotube and a molecular sieve composite for removing metal ions in ultra-pure ammonia. The composite is prepared by a chemical vapor-phase deposition process. The preparation method includes preparing carbon nanotubes on a mesoporous molecular sieve by the chemical vapor-phase deposition process and enabling the carbon nanotubes to grow on the surface and in holes of the mesoporous molecular sieve, to be bonded with the mesoporous molecular sieve firmly and to have excellent metal ion adsorption performance. The preparation method is simple; and the composite prepared by the preparation method is easy to replace and has good metal ion adsorption performance and conventional dehydrating and deoxidizing functions.
Description
Technical field
The present invention relates to go in a kind of gas generation the preparation method of deimpurity composition, particularly a kind of preparation method who removes the compound of metal ion in ultra-pure ammonia.
Background technology
In recent years, LED technology and the related industry of China have obtained fast development.Along with the fast development of the photoelectronic industries such as light emitting semiconductor device (LED), market has proposed requirements at the higher level to the purity of electronic gas.So greatly promoted the purification research of the crucial supplementary material ultra-pure ammonia in upstream.
7N electronic grade ultrapure ammonia is a kind of very important photoelectron material, is also the important foundation material that MOCVD technology is prepared GaN.In manufacturing light emitting diode (LED), flat-panel monitor (FPD), semiconductor and crystal silicon solar batteries sheet process, all need to use a large amount of ultra-pure ammonia, especially LED chip is in the time of growth, the purity of ammonia used is higher, the blue-ray LED power consumption of preparation is less, luminous intensity is larger, and service life is longer.7N electronic grade ultrapure ammonia is that LED crystal is manufactured the crucial supplementary material in important upstream, field thus, is the developing important step of industrial chain.
The gallium nitride that LED uses in producing is semi-conducting material, has two kinds of N-shaped p-types, so in process of production, strictly control the metal ion in raw material.But, the purifying process of at present both at home and abroad metal ion in ultra-pure ammonia being removed, be mainly utilize the physicochemical property of ammonia adopt multistep step by step purifying, comprise vaporization, condensation, absorption, rectifying, terminal purifying, the technology purification ammonia such as freezing.But the purifying process of these ultra-pure ammonia is conventionally to moisture and H
2, O
2, N
2, CH
4, CO, CO
2there is good effect Deng light component impurity, and remove undesirable to metal ion.
CNT is as relatively new adsorbent, and CNT has been proved to be has the great potential of removing metal ion from waste water as lead, cadmium, chromium, copper and mickel etc.CNT can be by electrostatic attraction, and the chemical action of the surface functional group of adsorption precipitation and metal ion and CNT, carrys out adsorbing metal ions.But CNT can not directly be positioned in ultra-pure ammonia, although can remove like this metal ion, after removing, CNT just can not separate with ultra-pure ammonia, can cause new pollution to ultra-pure ammonia.So will being attached to, CNT on other materials, carries out work, and in the purifying process of ultra-pure ammonia, itself just use molecular sieve, so just can play the effect of removing metal ion attached thereto CNT, can't cause secondary pollution to ultra-pure ammonia, can also save the cost that newly increases attachment material.
Summary of the invention
Goal of the invention of the present invention is in order to overcome the shortcoming in background technology, provides a kind of and can effectively remove the CNT of the metal ion in ultra-pure ammonia and the compound of molecular sieve and using method thereof,
Goal of the invention of the present invention is achieved by the following technical solution:
Remove the CNT of metal ion and a preparation method for molecular screen composite in ultra-pure ammonia, the method comprises the steps:
1) adopt infusion process to prepare the mesopore molecular sieve of load Fe, the Fe (NO of configuration 10%-30%
3)
3solution, fully dissolves it, then adds molecular sieve; This infusion process has detailed introduction at following publication: " nano material technology of preparing, Wang Shimin, Xu Zuxun, Fu Jing etc.Chemical Industry Press, Beijing, 2001." said mixture is placed in to the standing 5-12 h of air, after iron ion loads on mesopore molecular sieve, remove solution;
2) residue is dried and obtained Fe/ mesopore molecular sieve at 100-120 DEG C;
3) Fe/ mesopore molecular sieve is evenly laid in chemical vapour deposition reaction chamber, reaction chamber has resistance furnace heating outward;
4) capping chamber then starts to heat up under the protection of the protection gas of 1000-3000mL/ min flow, when temperature rises to 200-600 DEG C, passes into hydrogen with the flow of 30-300mL/ min;
5) after 1 hour, turn off hydrogen source gas, pass into C with the flow of 30-300mL/ min
2h
2carbon source is reacted 0. 5 hours at temperature 600-800 DEG C, after reaction finishes, turns off C
2h
2source of the gas;
6) make reaction system be cooled to room temperature in protection gas, take out mesopore molecular sieve, can obtain CNT/mesoporous molecular screen composite.
Described step 4) and 6) in protection gas be a kind of or its composition in argon gas or nitrogen or ammonia.
The compound finally obtaining is placed in the drier in ultra-pure ammonia prepurification stage, replaces the molecular sieve of the original common deoxygenation that dewaters.
The invention has the beneficial effects as follows: the carbon nano tube growth in compound of the present invention, in surface and the hole the inside of mesopore molecular sieve, in conjunction with firm, and has good adsorption of metal ions performance.It is simple that this preparation method has technique, easily changes, and the compound obtaining has good adsorption of metal ions performance, and has traditional deoxygenation function that dewaters.
Brief description of the drawings
Fig. 1 is preparation flow figure of the present invention;
Fig. 2 is CNT and molecular screen composite growth schematic diagram.
Detailed description of the invention
Detailed description of the invention
As shown in Figure 1, below by 2 embodiment, the present invention is described further for preparation flow of the present invention.
On molecular sieve, there are a lot of holes, have the A of vertical surface, have and favour surperficial B, also has the C of curved shape, can first deposit at the inner Fe ion of these holes, then CNT can be grown in these hole inside, finally forms CNT/mesoporous molecular screen composite.
Embodiment 1:
1) adopt infusion process to prepare the mesopore molecular sieve of load Fe, the Fe (NO of configuration 10%
3)
3solution, fully dissolves it, then adds molecular sieve;
2) said mixture is placed in to air and leaves standstill 6h, after iron ion loads on mesopore molecular sieve, remove solution;
3) residue is dried and obtained Fe/ mesopore molecular sieve at 100 DEG C;
4) Fe/ mesopore molecular sieve is evenly laid in chemical vapour deposition reaction chamber, reaction chamber has resistance furnace heating outward;
5) capping chamber then starts to heat up under the protection of the Ar of 1000mL/ min flow, when temperature rises to 200 DEG C, passes into hydrogen with the flow of 30mL/ min;
6) after 1 h, turn off hydrogen source gas, pass into C with the flow of 30mL/ min
2h
2carbon source is reacted 0. 5 h at 600 DEG C of temperature, after reaction finishes, turns off C
2h
2source of the gas;
7) make reaction system be cooled to room temperature in Ar atmosphere, take out mesopore molecular sieve, can obtain CNT/mesoporous molecular screen composite;
8) this compound is placed in the drier in ultra-pure ammonia prepurification stage, replaces the molecular sieve of the original common deoxygenation that dewaters.
Embodiment 2:
1) adopt infusion process to prepare the mesopore molecular sieve of load Fe, the Fe (NO of configuration 30%
3)
3solution, fully dissolves it, then adds molecular sieve;
2) said mixture is placed in to air and leaves standstill 10h, after iron ion loads on mesopore molecular sieve, remove solution;
3) residue is dried and obtained Fe/ mesopore molecular sieve at 120 DEG C;
4) Fe/ mesopore molecular sieve is evenly laid in chemical vapour deposition reaction chamber, reaction chamber has resistance furnace heating outward;
5) capping chamber then starts to heat up under the protection of the Ar of 2000mL/ min flow, when temperature rises to 300 DEG C, passes into hydrogen with the flow of 100mL/ min;
6) after 1 h, turn off hydrogen source gas, pass into C with the flow of 100mL/ min
2h
2carbon source is reacted 0. 5 h at 700 DEG C of temperature, after reaction finishes, turns off C
2h
2source of the gas;
7) make reaction system be cooled to room temperature in Ar atmosphere, take out mesopore molecular sieve, can obtain CNT/mesoporous molecular screen composite;
8) this compound is placed in the drier in ultra-pure ammonia prepurification stage, replaces the molecular sieve of the original common deoxygenation that dewaters.
Claims (2)
1. remove the CNT of metal ion and a preparation method for molecular screen composite in ultra-pure ammonia, it is characterized in that the method comprises the steps:
1) adopt infusion process to prepare the mesopore molecular sieve of load Fe, the Fe (NO of preparation 10%～30%
3)
3solution, fully dissolves it, then adds molecular sieve;
2) said mixture is placed in to air and leaves standstill 5-12 h, after iron ion loads on mesopore molecular sieve, remove solution;
3) residue is dried and obtained Fe/ mesopore molecular sieve at 100-120 DEG C;
4) Fe/ mesopore molecular sieve is evenly laid in chemical vapour deposition reaction chamber, reaction chamber has resistance furnace heating outward;
5) capping chamber then starts to heat up under the protection of the protection gas of 1000-3000mL/ min flow, when temperature rises to 200-600 DEG C, passes into hydrogen with the flow of 30-300mL/ min;
6) after 1 hour, turn off hydrogen source gas, pass into C with the flow of 30-300mL/ min
2h
2carbon source is reacted 0. 5 hours at temperature 600-800 DEG C, after reaction finishes, turns off C
2h
2source of the gas;
7) make reaction system be cooled to room temperature in protection gas, take out mesopore molecular sieve, can obtain CNT and molecular screen composite.
2. the CNT of metal ion and the preparation method of molecular screen composite in removal ultra-pure ammonia as claimed in claim 1, is characterized in that described step 5) and 7) in protection gas be a kind of or its composition in argon gas or nitrogen or ammonia.
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| CN102806068B true CN102806068B (en) | 2014-08-06 |
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| CN108079952A (en) * | 2016-03-31 | 2018-05-29 | 烟台智本知识产权运营管理有限公司 | The preparation method of the carbon nanotubes of metal ion/LDHs composite materials in a kind of absorption ultra-pure ammonia |
| CN106799206B (en) * | 2016-12-23 | 2020-02-21 | 句容亿格纳米材料厂 | Preparation method and application of carbon nanotube-molecular sieve compound |
| CN111921496A (en) * | 2020-07-10 | 2020-11-13 | 广东石油化工学院 | Composite adsorbent and preparation method and application thereof |
| CN111889076B (en) * | 2020-08-06 | 2022-08-12 | 北京金博威科技有限公司 | Adsorbent for removing virus or bacteria in gas, preparation method thereof, method and device for removing virus or bacteria in gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810639A (en) * | 2006-02-24 | 2006-08-02 | 中国人民解放军国防科学技术大学 | Chemical vapor deposition process of preparing Sic nanotube |
| CN1868589A (en) * | 2006-06-22 | 2006-11-29 | 厦门大学 | Method for preparing carbon nanometer tube/titanium dioxide composite photocatalyst |
| CN101244815A (en) * | 2008-03-17 | 2008-08-20 | 南京大学 | Method and device for producing carbon nano-tube or nitrogen doping carbon nano-tube with liquid phase forerunner article |
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| JP5120942B2 (en) * | 2008-04-03 | 2013-01-16 | 独立行政法人産業技術総合研究所 | Method for oxidative desulfurization of fuel oil using reaction rate difference and apparatus therefor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810639A (en) * | 2006-02-24 | 2006-08-02 | 中国人民解放军国防科学技术大学 | Chemical vapor deposition process of preparing Sic nanotube |
| CN1868589A (en) * | 2006-06-22 | 2006-11-29 | 厦门大学 | Method for preparing carbon nanometer tube/titanium dioxide composite photocatalyst |
| CN101244815A (en) * | 2008-03-17 | 2008-08-20 | 南京大学 | Method and device for producing carbon nano-tube or nitrogen doping carbon nano-tube with liquid phase forerunner article |
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| Title |
|---|
| JP特开2009-249447A 2009.10.29 |
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Address after: 215152 Anmin Road, Panyang Industrial Park, Huangdai Town, Xiangcheng District, Suzhou City, Jiangsu Province Patentee after: Jinhong Gas Co.,Ltd. Address before: 215143 No. 6 Anmin Road, Panyang Industrial Park, Huangduo Town, Xiangcheng District, Suzhou City, Jiangsu Province Patentee before: SUZHOU JINHONG GAS Co.,Ltd. |
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