CN102688744A - Preparation method of cerium supported active carbon - Google Patents
Preparation method of cerium supported active carbon Download PDFInfo
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- CN102688744A CN102688744A CN2011100714582A CN201110071458A CN102688744A CN 102688744 A CN102688744 A CN 102688744A CN 2011100714582 A CN2011100714582 A CN 2011100714582A CN 201110071458 A CN201110071458 A CN 201110071458A CN 102688744 A CN102688744 A CN 102688744A
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Abstract
The invention relates to a preparation method of a cerium supported active carbon, and belongs to the technical field of preparation of depth desulphurization catalyst for chemical fuel oil. The method is characterized by comprising the steps of: 1) dipping active carbon in a H2O2 solution at a room temperature, filtering out active carbon and drying the active carbon; 2) adding the active carbon into a cerium salting solution, stirring and dipping; and removing excessive solvent and drying the solution; and 3) placing the dried active carbon in a muffle furnace and cooling to obtain the cerium supported active carbon, wherein a mass content of cerium element is 0.35-3.5%. Compared with a prior art, the method of the invention has advantages of simple preparation technology and no special equipment; and the prepared active carbon has high stability and can substantially enhance adsorption performance on sulfur-containing compound. The method can be widely applied to fields of industrial adsorption desulphurization and production of ultra low sulfur fuel oil.
Description
Technical field:
The present invention relates to a kind of year cerium preparation method of active carbon, belong to petrochemical industry fuel oil deep desulfurization catalyst preparing technical field.
Background technology:
At present, comparatively ripe desulfurization of fuel oil technology is hydrodesulfurization in the industry.The sulfide of this desulfur technology in can the effective elimination petrol and diesel oil, but also can cause the reduction of combustibilities such as octane number, Cetane number simultaneously; And sweetening process needs the hydrogen of labor for facing H-H reaction, must under HTHP, carry out again, so equipment investment and operating cost ten minutes costliness; Especially to the condensed ring thiophene class sulfide that mainly contains in the petrol and diesel oil and derivative thereof (like 4-MDBT, 4; Removing 6-dimethyl Dibenzothiophene etc.) is very difficult; Process conditions require harsh, and also need use expensive noble metal catalyst.If want further hydrogenation carry out the refining depth desulfurization, produce and satisfy the super-low sulfur clean fuel that meets following environmental requirement, then the production cost that brings of hydrogen consumption, equipment investment and operating cost will sharply rise; In addition, the hydrogen sulfide that the aromatic hydrocarbons that contains in the oil product, nitride and hydrodesulfurization produce has very strong inhibitory action to reaction, also causes great difficulty to deep desulfuration.
Another kind of desulfur technology is an adsorption desulfurize.The sweetening process of adsorption desulfurize technology can be carried out under normal temperature and normal pressure; Have do not face hydrogen, simple to operate, equipment investment is few, pollution-free, the advantage of not losing octane number and diesel cetane-number; But production super-low sulfur fuel oil is especially more effective to the removing of fen class sulfide of exposing to the sun of condensed ring in the diesel oil.
The key of adsorption desulfurize technology is that a lot of adsorbents such as molecular sieve, aluminium oxide all have the ability that from oil product, removes sulfur-containing compound in the selection and preparation of adsorbent; Particularly active carbon can selective absorption a series of sulfur-containing compounds, like mercaptan, thioether, fen compounds etc. exposes to the sun; More hydrogen and oxygen are contained in active carbon inside, help chemical modification and are prepared into desulfurizing agent, the sulfide in the adsorbing and removing petrol and diesel oil; Absorbent charcoal based adsorbent has the good adsorption desulfurization performance because of having advantages such as specific area, surface active groups are abundant.
Summary of the invention:
In order to overcome the deficiency of prior art; The object of the present invention is to provide a kind of year cerium preparation method of active carbon; Its preparation technology simply, does not need special installation; Preparation carry cerium active carbon stability high, can significantly improve absorption property to sulfur-containing compound, can be widely used in industrial adsorption desulfurize and production super-low sulfur fuel oil field.
The present invention realizes above-mentioned purpose through following technical scheme.
A kind of year provided by the present invention cerium preparation method of active carbon comprises the steps:
1), with active carbon at H
2O
2Room temperature dipping in the solution leaches active carbon and oven dry then;
2), this active carbon is added stirring dipping in the cerium solution, evaporative removal excessive solvent and oven dry then;
3), the active carbon after will drying places Muffle furnace to calcine, and obtains after the cooling carrying a cerium active carbon, wherein the mass content of Ce elements is 0.35%--3.5%.
The H that described dipping is used
2O
2The concentration of solution is 20--40%; The consumption of solution is the H of the corresponding 10ml of per 1 gram active carbon
2O
2Solution, dipping temperature are 20--40 ℃, and dip time is 12--24 hour.
The used cerium solution of described dipping is (NH
4)
2Ce (NO
3)
6The aqueous solution or be Ce (NO
3)
3The aqueous solution, its concentration is 2.5--25mMol/L, the consumption of solution is the cerium solution of the corresponding 10ml of per 1 gram active carbon, dipping temperature is 20--40 ℃, dip time is 12--24 hour.
Describedly place Muffle furnace to calcine active carbon, the temperature of calcining is 300--400 ℃, and calcination time is 4--8 hour.
The present invention compared with prior art, its preparation technology simply, does not need special installation, preparation carry cerium active carbon stability high, can significantly improve absorption property to sulfur-containing compound, can be widely used in industrial adsorption desulfurize and production super-low sulfur fuel oil field.
The specific embodiment:
In order to understand the present invention better, the present invention is described further below in conjunction with specific embodiment:
Embodiment 1:
Choosing a kind of commercially available active carbon (be designated as AC1, Zhuxi, Jiangsu active carbon Co., Ltd produces), is 30% H in concentration
2O
2The room temperature dipping leached oven dry after 24 hours in the solution; Take by weighing the above-mentioned of every part of 10g through H
2O
2Four parts of the active carbons that solution-treated is crossed immerse 100ml concentration respectively and are 5,10,15, (the NH of 20mMol/L
4)
2Ce (NO
3)
6In the solution, stirring at room dipping is after 12 hours, and excessive solvent is through evaporative removal gradually in the environment about 50 ℃, and remaining solid 110 ℃ of oven dry in baking oven are spent the night.Dried sample places Muffle furnace to calcine, with the heating rate of 1 ℃/min be heated to 350 ℃ of insulations after 4 hours with the stove cooling, what obtain different cerium load capacity carries the cerium active carbon, is designated as successively: Ce1/AC1, Ce2/AC1, Ce3/AC1, Ce4/AC1.
Choose contain sulphur concentration be the octane solution of dibenzothiophenes of 500 μ g/g as the model fuel oil of desulfurization, prepared year cerium active carbon and original activity charcoal carry out desulfurization to the model fuel oil more than using respectively.Get every kind and carry each 0.75g of cerium acticarbon, respectively 20ml model fuel oil was adsorbed 24 hours result of the test such as following table under room temperature:
Embodiment 2:
Choosing a kind of commercially available active carbon (be designated as AC2, Shantou Xilong Chemical Industry Co., Ltd produces), is 30% H in concentration
2O
2The room temperature dipping leached oven dry after 24 hours in the solution; Take by weighing the above-mentioned of every part of 10g through H
2O
2Three parts of the active carbons that solution-treated is crossed immerse (the NH that 100ml concentration is 15mMol/L respectively
4)
2Ce (NO
3)
6In the solution, stirring at room dipping is after 12 hours, and excessive solvent is through evaporative removal gradually in the environment about 50 ℃, and remaining solid 110 ℃ of oven dry in baking oven are spent the night.Dried sample places Muffle furnace to calcine, and is heated to 300 ℃ respectively, 350 ℃ with the heating rate of 1 ℃/min; 400 ℃ of insulations were cooled off with stove after 4 hours, obtained year cerium active carbon of heat treatments at different, were designated as successively: 300Ce/AC2; 350Ce/AC2,400Ce/AC2.
Choose contain sulphur concentration be the octane solution of dibenzothiophenes of 500 μ g/g as the model fuel oil of desulfurization, prepared year cerium active carbon and original activity charcoal carry out desulfurization to the model fuel oil more than using respectively.Get every kind and carry each 0.75g of cerium acticarbon, respectively 20ml model fuel oil was adsorbed 24 hours result of the test such as following table under room temperature:
Embodiment 3:
Choosing the active carbon AC2 among the embodiment 2, is 30% H in concentration
2O
2The room temperature dipping leached oven dry after 24 hours in the solution, took by weighing the above-mentioned through H of every part of 10g
2O
2Four parts of the active carbons that solution-treated is crossed immerse 100ml concentration respectively and are 5,10,15, the Ce (NO of 20mMol/L
3)
3In the solution, stirring at room dipping is after 12 hours, and excessive solvent is through evaporative removal gradually in the environment about 50 ℃, and remaining solid 110 ℃ of oven dry in baking oven are spent the night.Dried sample places Muffle furnace to calcine, with the heating rate of 1 ℃/min be heated to 350 ℃ of insulations after 4 hours with the stove cooling, what obtain different cerium load capacity carries the cerium active carbon, is designated as successively: Ce 1/AC2, Ce2/AC2, Ce3/AC2, Ce4/AC2.
Choose contain sulphur concentration be the octane solution of dibenzothiophenes of 500 μ g/g as the model fuel oil of desulfurization, prepared year cerium active carbon and original activity charcoal carry out desulfurization to the model fuel oil more than using respectively.Every kind carries each 0.75g of cerium acticarbon, respectively 20ml model fuel oil was adsorbed 24 hours result of the test such as following table under room temperature:
Claims (5)
1. one kind carries the cerium preparation method of active carbon, it is characterized in that comprising the steps:
1), with active carbon at H
2O
2Room temperature dipping in the solution leaches active carbon and oven dry then;
2), this active carbon is added stirring dipping in the cerium solution, evaporative removal excessive solvent and oven dry then;
3), the active carbon after will drying places Muffle furnace to calcine, and obtains carrying a cerium active carbon after the cooling.
2. a kind of year according to claim 1 cerium preparation method of active carbon is characterized in that the H that described dipping is used
2O
2The concentration of solution is 20--40%; The consumption of solution is the H of the corresponding 10ml of per 1 gram active carbon
2O
2Solution, dipping temperature are 20--40 ℃, and dip time is 12--24 hour.
3. a kind of year according to claim 1 cerium preparation method of active carbon is characterized in that the used cerium solution of described dipping is (NH
4)
2Ce (NO
3)
6The aqueous solution or be Ce (NO
3)
3The aqueous solution, its concentration is 2.5--25mMol/L, the consumption of solution is the cerium solution of the corresponding 10ml of per 1 gram active carbon, dipping temperature is 20--40 ℃, dip time is 12--24 hour.
4. a kind of year according to claim 1 cerium preparation method of active carbon is characterized in that describedly placing Muffle furnace to calcine active carbon, and the temperature of calcining is 300--400 ℃, and calcination time is 4--8 hour.
5. according to claim 2,3,4 described a kind of year cerium preparation method of active carbon, it is characterized in that the described mass content that obtains Ce elements in year cerium active carbon is 0.35%--3.5%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170131A (en) * | 2015-09-10 | 2015-12-23 | 广州中国科学院先进技术研究所 | Preparation method of novel sludge carbon-based desulfurization and denitrification catalyst |
| CN113441109A (en) * | 2021-06-07 | 2021-09-28 | 南通大学 | Preparation method of compound modified spherical activated carbon for gas defense |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101601998A (en) * | 2009-06-11 | 2009-12-16 | 浙江省环境保护科学设计研究院 | A kind of Preparation of catalysts method that is used for treating high-concentration organic wastewater through catalytic oxidation |
| CN101804325A (en) * | 2010-04-22 | 2010-08-18 | 上海化工研究院 | Preparation method of modified activated carbon adsorption desulfurizing agent |
| EP1828447B1 (en) * | 2004-11-16 | 2011-01-26 | Hyperion Catalysis International, Inc. | Method for preparing supported catalysts from metal loaded carbon nanotubes |
-
2011
- 2011-03-24 CN CN2011100714582A patent/CN102688744A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1828447B1 (en) * | 2004-11-16 | 2011-01-26 | Hyperion Catalysis International, Inc. | Method for preparing supported catalysts from metal loaded carbon nanotubes |
| CN101601998A (en) * | 2009-06-11 | 2009-12-16 | 浙江省环境保护科学设计研究院 | A kind of Preparation of catalysts method that is used for treating high-concentration organic wastewater through catalytic oxidation |
| CN101804325A (en) * | 2010-04-22 | 2010-08-18 | 上海化工研究院 | Preparation method of modified activated carbon adsorption desulfurizing agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170131A (en) * | 2015-09-10 | 2015-12-23 | 广州中国科学院先进技术研究所 | Preparation method of novel sludge carbon-based desulfurization and denitrification catalyst |
| CN113441109A (en) * | 2021-06-07 | 2021-09-28 | 南通大学 | Preparation method of compound modified spherical activated carbon for gas defense |
| CN113441109B (en) * | 2021-06-07 | 2023-11-07 | 南通大学 | Preparation method of composite modified spherical active carbon for gas defense |
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Application publication date: 20120926 |