JP2018510768A - Multi-walled carbon nanotube catalyst, its production method and its use - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 13
- 230000023556 desulfurization Effects 0.000 claims abstract description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 12
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical group [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000003546 flue gas Substances 0.000 abstract description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000003245 coal Substances 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/34—Chemical or biological purification of waste gases
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
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Abstract
【課題】【解決手段】本発明は、排煙脱硫の分野に属する。詳細には、本発明は、複層カーボン・ナノチューブ触媒、その製造方法、およびその使用に関する。前記触媒は、複層カーボン・ナノチューブを支持体として用い、硝酸コバルトと硝酸マンガンを触媒的活性成分として用いる。その製造方法は、以下のとおりである：前記複層カーボン・ナノチューブを硝酸中で還流加熱し、次いで、吸引によるろ過を行い、中性まで洗浄し、次いで乾燥し、そして、硝酸マンガンおよび硝酸コバルトの混合溶液への添加が続き、超音波で分散し、乾燥し、粉砕し、Ｎ2雰囲気下で焼成することにより変性させて、前記複層カーボン・ナノチューブ触媒を得る。前記触媒は、少量で用いられ、回収が容易であり、優れた触媒効果を有し、２次汚染問題が無く、石炭燃焼排煙脱硫の副生成物酸化システムにおいて広く用いることができ；前記触媒は、通常の酸化方法が実質的に変化していない条件で、５０％以上も、亜硝酸塩の酸化率を向上させることができる。【選択図】 図１The present invention belongs to the field of flue gas desulfurization. In particular, the present invention relates to a multi-walled carbon nanotube catalyst, a method for its production, and its use. The catalyst uses multi-walled carbon nanotubes as a support and cobalt nitrate and manganese nitrate as catalytic active components. The production method is as follows: the multi-walled carbon nanotubes are heated to reflux in nitric acid, then filtered by suction, washed to neutrality, then dried, and manganese nitrate and cobalt nitrate Is added to the mixed solution, dispersed by ultrasonic waves, dried, pulverized, and modified by calcination in an N2 atmosphere to obtain the multi-walled carbon nanotube catalyst. The catalyst is used in a small amount, is easy to recover, has an excellent catalytic effect, has no secondary pollution problem, and can be widely used in a by-product oxidation system of coal combustion flue gas desulfurization; Can improve the oxidation rate of nitrite by 50% or more under the condition that the normal oxidation method is not substantially changed. [Selection] Figure 1
Description
本発明は、排煙脱硫の分野に関する。詳細には、本発明は、複層カーボン・ナノチューブ触媒と、その製造方法およびその使用に関する。 The present invention relates to the field of flue gas desulfurization. In particular, the present invention relates to multi-walled carbon nanotube catalysts, methods for their production and uses thereof.
ＳＯ2は、公害関係現象の酸性雨および煙霧を生じる重要な前駆体であり、近年、国内空環境への多大な損害を引き起こしてきた。現時点で、排煙湿式脱硫が、最も経済的かつ効果的な脱硫方法であるが、副生成物の亜硫酸塩の酸化反応率が比較的低く、脱硫副生物の回収方法の比較的高い投資とエネルギー消費を生じ；亜硫酸塩の不十分な酸化は、システム拡大縮小、ブロッキング、低い生成物品質、流出物の二次汚染等の問題を引き起こす傾向があった。 SO 2 is an important precursor that generates acid rain and haze of pollution-related phenomena, and has recently caused significant damage to the domestic air environment. At present, flue gas wet desulfurization is the most economical and effective desulfurization method, but the oxidation rate of by-product sulfite is relatively low and desulfurization by-product recovery method is relatively high investment and energy Insufficient oxidation of sulfite tended to cause problems such as system scaling, blocking, low product quality, effluent cross-contamination.
ここで、脱硫システムの不十分な酸化能力という問題を解決するための主な手段は、金属イオン型触媒を添加し、亜硫酸塩の酸化率を増加させることである。しかし、前記触媒を脱硫スラリーへ溶液の形態で添加すると、適用方法の操作コストが高くなる；一方、回収するのが困難な前記触媒は、脱硫副生成物および廃液における重金属の二次汚染を引き起こす。従って、前記触媒の適用および普及は、非常に限定的である。 Here, the main means for solving the problem of insufficient oxidation capacity of the desulfurization system is to add a metal ion type catalyst to increase the oxidation rate of sulfite. However, adding the catalyst in the form of a solution to the desulfurization slurry increases the operating cost of the application method; while the catalyst, which is difficult to recover, causes secondary contamination of desulfurization by-products and heavy metals in the waste liquor. . Therefore, the application and spread of the catalyst is very limited.
［発明の要旨］
液状金属イオン型触媒の欠点を解消するため、本発明は、複層カーボン・ナノチューブ触媒、その製造方法およびその使用を提供する。詳細には、技術的解決策は以下のとおりである。
[Summary of the Invention]
In order to eliminate the disadvantages of the liquid metal ion type catalyst, the present invention provides a multi-walled carbon nanotube catalyst, a production method thereof and a use thereof. In detail, the technical solutions are as follows.
複層カーボン・ナノチューブ触媒が、複層カーボン・ナノチューブを支持体として用い、硝酸コバルトおよび硝酸マンガンを触媒的活性成分として用いることにより、提供される。 Multi-walled carbon nanotube catalysts are provided by using multi-walled carbon nanotubes as a support and cobalt nitrate and manganese nitrate as catalytically active components.
好ましくは、前記複層カーボン・ナノチューブは、以下の４つのサイズを有する：
（１）直径：１０〜２０ｎｍ、内径：５〜１０ｎｍ、チューブ長さ：１０〜３０μｍ；
（２）直径：２０〜３０ｎｍ、内径：５〜１０ｎｍ、チューブ長さ：１０〜３０μｍ；
（３）直径：３０〜５０ｎｍ、内径：５〜１２ｎｍ、チューブ長さ：１０〜２０μｍ；
（４）直径：＞５０ｎｍ、内径：５〜１５ｎｍ、チューブ長さ：１０〜２０μｍ。
Preferably, the multi-walled carbon nanotube has the following four sizes:
(1) Diameter: 10-20 nm, inner diameter: 5-10 nm, tube length: 10-30 μm;
(2) Diameter: 20-30 nm, inner diameter: 5-10 nm, tube length: 10-30 μm;
(3) Diameter: 30-50 nm, inner diameter: 5-12 nm, tube length: 10-20 μm;
(4) Diameter:> 50 nm, inner diameter: 5-15 nm, tube length: 10-20 μm.
前記触媒を製造する方法は、以下のとおりである。前記複層カーボン・ナノチューブは、硝酸中で還流加熱し、次いで、吸引によるろ過を行い、中性まで洗浄し、次いで、乾燥し、そして、硝酸マンガンおよび硝酸コバルトの混合溶液への添加が続き、超音波で分散し、乾燥し、粉砕し、Ｎ2雰囲気下で焼成することにより変性させて、前記複層カーボン・ナノチューブ触媒を得る。 The method for producing the catalyst is as follows. The multi-walled carbon nanotubes are heated to reflux in nitric acid, then filtered by suction, washed to neutrality, then dried, followed by addition to a mixed solution of manganese nitrate and cobalt nitrate, The multilayer carbon nanotube catalyst is obtained by being dispersed by ultrasonic waves, dried, pulverized, and modified by firing in an N 2 atmosphere.
詳細には、これらの工程は：
（１）前記複層カーボン・ナノチューブを硝酸溶液中に浸漬させ、攪拌し、加熱し、５〜７時間還流加熱し、吸引によりろ過し、中性まで洗浄し、乾燥して、変性複層カーボン・ナノチューブを得る工程；
（２）前記変性複層カーボン・ナノチューブを、硝酸マンガンおよび硝酸コバルトの混合無水エタノール溶液へ浸漬させ、電磁力で２〜３時間攪拌する工程；
（３）工程（２）で得た前記複層カーボン・ナノチューブを２０〜４０分間超音波で分散せ、乾燥する工程；
（４）工程（３）で得た前記複層カーボン・ナノチューブを粉砕し、Ｎ2保護雰囲気下で焼成して、前記複層カーボン・ナノチューブ触媒を得る工程。
In detail, these steps are:
(1) The multi-walled carbon nanotube is immersed in a nitric acid solution, stirred, heated, heated to reflux for 5 to 7 hours, filtered by suction, washed to neutrality, dried, and modified multi-walled carbon. A step of obtaining nanotubes;
(2) A step of immersing the modified multi-walled carbon nanotube in a mixed anhydrous ethanol solution of manganese nitrate and cobalt nitrate and stirring for 2 to 3 hours by electromagnetic force;
(3) Dispersing the multi-walled carbon nanotubes obtained in step (2) with ultrasonic waves for 20 to 40 minutes and drying;
(4) A step of pulverizing the multi-walled carbon nanotubes obtained in the step (3) and firing in a N 2 protective atmosphere to obtain the multi-walled carbon nanotube nanotube catalyst.
好ましくは、前記混合無水エタノール溶液中、硝酸マンガンの濃度は、０．００１ｍｏｌ／Ｌ〜０．０７２ｍｏｌ／Ｌの範囲であり、硝酸コバルトの濃度は、０．００１９ｍｏｌ／Ｌ〜０．０６８ｍｏｌ／Ｌの範囲であり、硝酸コバルトに対する硝酸マンガンのモル比は、（０．０５〜０．９５）：１である。 Preferably, in the mixed absolute ethanol solution, the concentration of manganese nitrate is in the range of 0.001 mol / L to 0.072 mol / L, and the concentration of cobalt nitrate is 0.0019 mol / L to 0.068 mol / L. The molar ratio of manganese nitrate to cobalt nitrate is (0.05-0.95): 1.
好ましくは、工程（１）および（２）において、前記攪拌は、磁気攪拌機を用いて行われ、その回転率は、１００ｒ／分である。 Preferably, in steps (1) and (2), the stirring is performed using a magnetic stirrer, and the rotation rate is 100 r / min.
好ましくは、工程（１）および（３）において、乾燥温度は、８０℃〜１２０℃の範囲であり、乾燥時間は、２時間〜３時間の範囲であり；工程（４）において、焼成温度は、４００℃〜５００℃の範囲であり、焼成時間は、３時間〜５時間の範囲である。 Preferably, in steps (1) and (3), the drying temperature is in the range of 80 ° C. to 120 ° C., the drying time is in the range of 2 hours to 3 hours; in step (4), the firing temperature is The baking time is in the range of 3 hours to 5 hours.
上記触媒の適用は、前記触媒を湿式脱硫システムの吸収スラリーへ添加し、亜硫酸塩の酸化を触媒することであり；前記吸収スラリーにおいて、亜硫酸塩の濃度は、１０ｇ／Ｌ〜１６０ｇ／Ｌの範囲である。 Application of the catalyst is to add the catalyst to the absorbent slurry of a wet desulfurization system to catalyze the oxidation of sulfite; in the absorbent slurry, the concentration of sulfite ranges from 10 g / L to 160 g / L It is.
好ましくは、前記亜硫酸塩は、亜硫酸マグネシウムである。 Preferably, the sulfite is magnesium sulfite.
本発明の製造方法は、簡単で操作が容易であり、優れた効果を有する；従来技術と比較して、本発明は、以下の利点を有する：
（１）本発明による亜硫酸塩の酸化を促進するための、前記複層カーボン・ナノチューブは、安価であり、容易に入手可能であり、前記触媒の製造方法は簡単であり、前記触媒は、その触媒率（速度）に影響を与えることなく、成形技術により、さまざまな形やサイズに成形することが可能である；
（２）本発明の前記触媒は、優れた触媒効果を有し、湿式脱硫方法の酸化システムの最適化において、有効に用いることができる；前記触媒の適用は、脱硫システムに悪い影響を与えず、同時に、亜硫酸マグネシウムの酸化率を５０％以上に増加させる。
（３）前記触媒の活性成分は、少量で用いられるが、高い効力を有し、二次汚染問題は、有効に避けられる。
The production method of the present invention is simple and easy to operate and has excellent effects; compared with the prior art, the present invention has the following advantages:
(1) The multi-walled carbon nanotube for promoting oxidation of sulfite according to the present invention is inexpensive and easily available, and the method for producing the catalyst is simple. Various shapes and sizes can be formed by molding technology without affecting the catalyst rate (speed);
(2) The catalyst of the present invention has an excellent catalytic effect and can be used effectively in optimizing the oxidation system of the wet desulfurization method; the application of the catalyst does not adversely affect the desulfurization system At the same time, the oxidation rate of magnesium sulfite is increased to 50% or more.
(3) Although the active component of the catalyst is used in a small amount, it has high efficacy and the secondary contamination problem is effectively avoided.
本発明の適用方法をより明確に説明するため、以下の実施例は例示であり、本発明の保護範囲を限定するためのものではない。 In order to explain the application method of the present invention more clearly, the following examples are illustrative and are not intended to limit the protection scope of the present invention.
亜硫酸マグネシウムの酸化促進のため、以下の実施例で用いられる前記複層カーボン・ナノチューブ触媒は、前処理される必要があり、詳細には、以下の工程で前処理される必要がある：前記複層カーボン・ナノチューブは、６０％硝酸中で、１００ｒ／分の回転率で磁気的に攪拌され、加熱され、５〜７時間還流加熱され、吸引によりろ過し、中性まで洗浄し、１２０℃で２時間乾燥して、変性複層カーボン・ナノチューブを得た。 In order to promote the oxidation of magnesium sulfite, the multi-walled carbon nanotube catalyst used in the following examples needs to be pretreated, in particular, it needs to be pretreated in the following steps: Single-wall carbon nanotubes are magnetically stirred and heated in 60% nitric acid at a rotation rate of 100 r / min, heated to reflux for 5-7 hours, filtered by suction, washed to neutrality, at 120 ° C. After drying for 2 hours, modified multi-walled carbon nanotubes were obtained.
触媒条件下での亜硫酸マグネシウムの反応速度を測定する方法は、以下のとおりである：ある量の前記触媒を、亜硫酸マグネシウムの酸化反応システム中に添加し、反応条件は以下のとおりである：反応溶液量：２００ｍｌ、反応温度：４５℃、亜硫酸マグネシウムの当初濃度：２０ｇ／Ｌ、ｐＨ：８．０、強制空気流速：６０Ｌ／時間。反応器中の硫酸塩イオンの濃度は、間隔をおいて試験し、単位時間における硫酸塩イオンの生成量は、亜硫酸マグネシウムの酸化反応率を示し、触媒条件下での亜硫酸マグネシウムの反応率は、そのようにして得た。 A method for measuring the reaction rate of magnesium sulfite under catalytic conditions is as follows: an amount of the catalyst is added into the magnesium sulfite oxidation reaction system, and the reaction conditions are as follows: reaction Amount of solution: 200 ml, reaction temperature: 45 ° C., initial concentration of magnesium sulfite: 20 g / L, pH: 8.0, forced air flow rate: 60 L / hour. The concentration of sulfate ion in the reactor was tested at intervals, the amount of sulfate ion produced per unit time indicates the oxidation reaction rate of magnesium sulfite, and the reaction rate of magnesium sulfite under catalytic conditions is So obtained.
［実施例1］
亜硫酸マグネシウムの酸化反応システムにおいて、添加剤は添加せず、反応溶液量は、２００ｍｌであり、反応温度は４５℃であり、亜硫酸マグネシウムの当初濃度は２０ｇ／Ｌであり、ｐＨは、８．０であり、強制空気流速は、６０Ｌ／時間であり、そのような条件下で、反応速度は、図１においてケース０に示すように、０．０１０７７ｍｍｏｌ／（Ｌ・ｓ）であった。
[Example 1]
In the magnesium sulfite oxidation reaction system, no additive was added, the reaction solution volume was 200 ml, the reaction temperature was 45 ° C., the initial concentration of magnesium sulfite was 20 g / L, and the pH was 8.0. The forced air flow rate was 60 L / hour, and under such conditions, the reaction rate was 0.01077 mmol / (L · s) as shown in case 0 in FIG.
［実施例２］
前処理の後、直径１０〜２０ｎｍ、内径５〜１０ｎｍおよびチューブ長さ１０〜３０μｍの前記複層カーボン・ナノチューブ２．０００ｇを、Ｍｎ（ＮＯ3）2・４Ｈ2Ｏの濃度０．００８５ｍｏｌ／ＬおよびＣｏ（ＮＯ3）2・６Ｈ2Ｏの濃度０．００９１ｍｏｌ／Ｌ（前記２者のモル比は、２／３である）の溶液へ添加し、その後、温度自動調節の磁気攪拌機を用いて、２時間の間、１００ｒ／分で動力学的浸漬を行い、３０分間超音波分散を行い、８０℃で３時間乾燥し、粉砕し、Ｎ2保護の下、１２０℃まで温度を上げ、１時間保持し、さらに、４５０℃まで温度を上げ、５時間焼成し、亜硫酸マグネシウムの酸化を向上させるための複層カーボン・ナノチューブ触媒を得た。
[Example 2]
After the pretreatment, 2.000 g of the multi-walled carbon nanotube having a diameter of 10 to 20 nm, an inner diameter of 5 to 10 nm and a tube length of 10 to 30 μm was added to a Mn (NO 3 ) 2 .4H 2 O concentration of 0.0085 mol / L. And Co (NO 3 ) 2 · 6H 2 O to a solution having a concentration of 0.0091 mol / L (the molar ratio of the two is 2/3), and then using a temperature-adjusted magnetic stirrer Dynamic soaking at 100 r / min for 2 hours, ultrasonic dispersion for 30 minutes, drying at 80 ° C. for 3 hours, grinding, raising the temperature to 120 ° C. under N 2 protection, This was maintained for a period of time, and the temperature was further raised to 450 ° C., followed by firing for 5 hours to obtain a multi-walled carbon nanotube catalyst for improving the oxidation of magnesium sulfite.
０．２ｇの得られた触媒を、反応溶液量２００ｍｌの亜硫酸マグネシウムの酸化反応システムへ添加した。ここで、触媒反応速度は、図１においてケース１により示されるように０．０４８８４ｍｍｏｌ／（Ｌ・ｓ）であり、非触媒条件と比較して、３．５３倍増加した。
0.2 g of the resulting catalyst was added to a magnesium sulfite oxidation reaction system with a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.04884 mmol / (L · s) as shown by
［実施例３］
前処理の後、直径２０〜３０ｎｍ、内径５〜１０ｎｍおよびチューブ長さ１０〜３０μｍの前記複層カーボン・ナノチューブ２．０００ｇを、Ｍｎ（ＮＯ3）2・４Ｈ2Ｏの濃度０．０１２６ｍｏｌ／ＬおよびＣｏ（ＮＯ3）2・６Ｈ2Ｏの濃度０．０１７９ｍｏｌ／Ｌ（前記２者のモル比は、１／４である）の溶液へ添加し、温度自動調節の磁気攪拌機を用いて、２時間の間、１００ｒ／分で動力学的浸漬を行い、４０分間超音波分散を行い、８０℃で２時間乾燥し、粉砕し、Ｎ2保護の下、１２０℃まで温度を上げ、１時間保持し、さらに、５００℃まで温度を上げ、３時間焼成し、亜硫酸マグネシウムの酸化を向上させるための複層カーボン・ナノチューブ触媒を得た。
[Example 3]
After the pretreatment, 2.000 g of the multi-walled carbon nanotubes having a diameter of 20 to 30 nm, an inner diameter of 5 to 10 nm and a tube length of 10 to 30 μm were added to a Mn (NO 3 ) 2 .4H 2 O concentration of 0.0126 mol / L. And Co (NO 3 ) 2 .6H 2 O having a concentration of 0.0179 mol / L (the molar ratio of the two is 1/4), and using a magnetic stirrer with automatic temperature control, 2 Dynamic soaking at 100r / min for time, ultrasonic dispersion for 40 minutes, drying at 80 ° C for 2 hours, grinding, raising temperature to 120 ° C under N 2 protection and holding for 1 hour Further, the temperature was raised to 500 ° C. and calcined for 3 hours to obtain a multi-walled carbon nanotube catalyst for improving the oxidation of magnesium sulfite.
０．４ｇの得られた触媒を、反応溶液量２００ｍｌの亜硫酸マグネシウムの酸化反応システムへ添加した。ここで、触媒反応速度は、図１においてケース２により示されるように、０．０５７８５ｍｍｏｌ／（Ｌ・ｓ）であり、非触媒条件と比較して、４．３７倍増加した。 0.4 g of the resulting catalyst was added to a magnesium sulfite oxidation reaction system with a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.05785 mmol / (L · s), as shown by case 2 in FIG. 1, and increased by 4.37 times compared to the non-catalytic condition.
［実施例4］
前処理の後、直径３０〜５０ｎｍ、内径５〜１２ｎｍおよびチューブ長さ１０〜２０μｍの前記複層カーボン・ナノチューブ２．０００ｇを、Ｍｎ（ＮＯ3）2・４Ｈ2Ｏの濃度０．０２５８ｍｏｌ／ＬおよびＣｏ（ＮＯ3）2・６Ｈ2Ｏの濃度０．０２３５ｍｏｌ／Ｌ（前記２者のモル比は、３／５である）の溶液へ添加し、温度自動調節の磁気攪拌機を用いて、３時間の間、１００ｒ／分で動力学的浸漬を行い、２０分間超音波分散を行い、１２０℃で３時間乾燥し、粉砕し、Ｎ2保護の下、１２０℃まで温度を上げ、１時間保持し、さらに、４００℃まで温度を上げ、５時間焼成し、亜硫酸マグネシウムの酸化を向上させるための複層カーボン・ナノチューブ触媒を得た。
[Example 4]
After the pretreatment, 2.000 g of the multi-walled carbon nanotube having a diameter of 30 to 50 nm, an inner diameter of 5 to 12 nm and a tube length of 10 to 20 μm was added to a Mn (NO 3 ) 2 .4H 2 O concentration of 0.0258 mol / L. And Co (NO 3 ) 2 .6H 2 O having a concentration of 0.0235 mol / L (the molar ratio of the two is 3/5), and using a magnetic stirrer with automatic temperature control, 3 Dynamic soaking at 100 r / min for 20 hours, ultrasonic dispersion for 20 minutes, drying at 120 ° C. for 3 hours, grinding, raising temperature to 120 ° C. under N 2 protection and holding for 1 hour Further, the temperature was raised to 400 ° C. and calcined for 5 hours to obtain a multi-walled carbon nanotube catalyst for improving the oxidation of magnesium sulfite.
０．２５ｇの得られた触媒を、反応溶液量２００ｍｌの亜硫酸マグネシウムの酸化反応システムへ添加した。ここで、触媒反応速度は、図１においてケース３により示されるように、０．０５８４７ｍｍｏｌ／（Ｌ・ｓ）であり、非触媒条件と比較して、４．４３倍増加した。 0.25 g of the resulting catalyst was added to a magnesium sulfite oxidation reaction system with a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.05847 mmol / (L · s) as shown by case 3 in FIG. 1, and increased by 4.43 times compared to the non-catalytic condition.
［実施例５］
前処理の後、直径＞５０ｎｍ、内径５〜１５ｎｍおよびチューブ長さ１０〜２０μｍの前記複層カーボン・ナノチューブ２．０００ｇを、Ｍｎ（ＮＯ3）2・４Ｈ2Ｏの濃度０．０３８２ｍｏｌ／ＬおよびＣｏ（ＮＯ3）2・６Ｈ2Ｏの濃度０．０３６０ｍｏｌ／Ｌ（前記２者のモル比は、４／７である）の溶液へ添加し、温度自動調節の磁気攪拌機を用いて、２．５時間の間、１００ｒ／分で動力学的浸漬を行い、３０分間超音波分散を行い、１２０℃で２時間乾燥し、粉砕し、Ｎ2保護の下、１２０℃まで温度を上げ、１時間保持し、さらに、４５０℃まで温度を上げ、４時間焼成し、亜硫酸マグネシウムの酸化を向上させるための、複層カーボン・ナノチューブ触媒を得た。
[Example 5]
After the pretreatment, 2.000 g of the above-mentioned multi-walled carbon nanotubes having a diameter> 50 nm, an inner diameter of 5 to 15 nm and a tube length of 10 to 20 μm were added to a Mn (NO 3 ) 2 .4H 2 O concentration of 0.0382 mol / L and 1. Add to a solution of Co (NO 3 ) 2 .6H 2 O concentration of 0.0360 mol / L (the molar ratio of the two is 4/7) and use a magnetic stirrer with automatic temperature control. Dynamic soaking at 100 r / min for 5 hours, ultrasonic dispersion for 30 minutes, drying at 120 ° C. for 2 hours, grinding, raising temperature to 120 ° C. under N 2 protection, 1 hour Then, the temperature was raised to 450 ° C. and calcined for 4 hours to obtain a multi-wall carbon nanotube catalyst for improving the oxidation of magnesium sulfite.
０．３ｇの得られた触媒を、反応溶液量２００ｍｌの亜硫酸マグネシウムの酸化反応システムへ添加した。ここで、触媒反応速度は、図１においてケース４により示されるように、０．０６２５９ｍｍｏｌ／（Ｌ・ｓ）であり、非触媒条件と比較して、４．８１倍増加した。 0.3 g of the resulting catalyst was added to a magnesium sulfite oxidation reaction system with a reaction solution volume of 200 ml. Here, the catalytic reaction rate was 0.06259 mmol / (L · s), as shown by case 4 in FIG. 1, and increased by 4.81 times compared to the non-catalytic condition.
Claims (9)
（１）直径：１０〜２０ｎｍ、内径：５〜１０ｎｍ、チューブ長さ：１０〜３０μｍ；
（２）直径：２０〜３０ｎｍ、内径：５〜１０ｎｍ、チューブ長さ：１０〜３０μｍ；
（３）直径：３０〜５０ｎｍ、内径：５〜１２ｎｍ、チューブ長さ：１０〜２０μｍ；
（４）直径：＞５０ｎｍ、内径：５〜１５ｎｍ、チューブ長さ：１０〜２０μｍ
を有する請求項１に記載の触媒。 The multi-walled carbon nanotube has four sizes:
(1) Diameter: 10-20 nm, inner diameter: 5-10 nm, tube length: 10-30 μm;
(2) Diameter: 20-30 nm, inner diameter: 5-10 nm, tube length: 10-30 μm;
(3) Diameter: 30-50 nm, inner diameter: 5-12 nm, tube length: 10-20 μm;
(4) Diameter:> 50 nm, inner diameter: 5-15 nm, tube length: 10-20 μm
The catalyst of claim 1 having
前記複層カーボン・ナノチューブは、硝酸中で還流加熱し、次いで、吸引によるろ過を行い、中性まで洗浄し、次いで、乾燥し、そして硝酸マンガンおよび硝酸コバルトの混合溶液への添加が続き、超音波で分散し、乾燥し、粉砕し、Ｎ2雰囲気で焼成することにより変性させて、前記複層カーボン・ナノチューブ触媒を得ることを特徴とする方法。 A method for producing the catalyst according to claim 1, comprising:
The multi-walled carbon nanotubes are heated to reflux in nitric acid, then filtered by suction, washed to neutrality, then dried, followed by addition to a mixed solution of manganese nitrate and cobalt nitrate, A method characterized in that the multi-walled carbon nanotube catalyst is obtained by dispersing with sonic waves, drying, pulverizing, and modifying by firing in an N 2 atmosphere.
（１）前記複層カーボン・ナノチューブを硝酸溶液中に浸漬させ、攪拌し、加熱し、５〜７時間還流加熱し、吸引によりろ過し、中性まで洗浄し、乾燥して、変性複層カーボン・ナノチューブを得る行程、
（２）前記変性複層カーボン・ナノチューブを、硝酸マンガンおよび硝酸コバルトの混合無水エタノール溶液へ浸漬させ、電磁力で２〜３時間攪拌する行程、
（３）行程（２）で得た前記複層カーボン・ナノチューブを２０〜４０分間超音波で分散させ、乾燥する行程、
（４）行程（３）で得た前記複層カーボン・ナノチューブを粉砕し、Ｎ2保護雰囲気下で焼成して、前記複層カーボン・ナノチューブ触媒を得る行程。 The method of claim 3 characterized by the following specific steps:
(1) The multi-walled carbon nanotube is immersed in a nitric acid solution, stirred, heated, heated to reflux for 5 to 7 hours, filtered by suction, washed to neutrality, dried, and modified multi-walled carbon.・ The process of obtaining nanotubes,
(2) a step of immersing the modified multi-walled carbon nanotube in a mixed anhydrous ethanol solution of manganese nitrate and cobalt nitrate and stirring with electromagnetic force for 2 to 3 hours;
(3) a step of dispersing the multi-walled carbon nanotubes obtained in step (2) with ultrasonic waves for 20 to 40 minutes and drying;
(4) A step of pulverizing the multi-walled carbon nanotubes obtained in step (3) and firing in a N 2 protective atmosphere to obtain the multi-walled carbon nanotube catalyst.
硝酸マンガンの濃度は、０．００１ｍｏｌ／Ｌ〜０．０７２ｍｏｌ／Ｌの範囲であり、
硝酸コバルトの濃度は、０．００１９ｍｏｌ／Ｌ〜０．０６８ｍｏｌ／Ｌの範囲であり、
硝酸コバルトに対する硝酸マンガンのモル比は、（０．０５〜０．９５）：１である請求項４に記載の方法。 In the mixed absolute ethanol solution,
The concentration of manganese nitrate is in the range of 0.001 mol / L to 0.072 mol / L,
The concentration of cobalt nitrate is in the range of 0.0019 mol / L to 0.068 mol / L,
The process according to claim 4, wherein the molar ratio of manganese nitrate to cobalt nitrate is (0.05-0.95): 1.
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| WO2023277350A1 (en) * | 2021-06-30 | 2023-01-05 | 주식회사 제이오 | Method for manufacturing carbon nanotube dispersion |
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| CN107107038A (en) | 2017-08-29 |
| CN107107038B (en) | 2020-01-03 |
| WO2017024421A1 (en) | 2017-02-16 |
| JP6495470B2 (en) | 2019-04-03 |
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