CN1224033A - Method for preparing asphalt based spherical active carbon by adding inorganic metal salt - Google Patents

Method for preparing asphalt based spherical active carbon by adding inorganic metal salt Download PDF

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Publication number
CN1224033A
CN1224033A CN 98104731 CN98104731A CN1224033A CN 1224033 A CN1224033 A CN 1224033A CN 98104731 CN98104731 CN 98104731 CN 98104731 A CN98104731 A CN 98104731A CN 1224033 A CN1224033 A CN 1224033A
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organic solvent
asphalt
inorganic salt
water
pitch
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CN 98104731
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CN1089097C (en
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刘朗
刘植昌
凌立成
乔文明
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

A process for preparing spherical asphalt-base activated carbon by adding inorganic metal salt includes preparing the aqueous solution of inorganic salt, adding organic solvent able to dissolve asphalt and having mutual solubility with water, high-temp (100-300 deg.C) mixing with asphalt proportionally in high-pressure tank, high-temp or vacuum extracting to remove water and organic solvent, high-temp (100-300 deg.C) mixing with aromatic solvent proportionally in a high-pressure tank, granulating by emulsifying, non-melting treatment, charring and activating. Its advantages are high activity, uniform granularity, high roundness and strength, low resistance and quick adsorption and desorption.

Description

The interpolation metal inorganic salt prepares the method for asphalt-base globular active carbon
The invention belongs to a kind of preparation method of gac, being specifically related to a kind of is that raw material adds the method that metal inorganic salt prepares spheric active carbon with pitch.
Characteristics such as the little and adsorption desorption speed of asphalt-base globular active carbon has good sphericity, physical strength height, fixed bed when using resistance is fast have obtained using widely in fields such as environmental protection, medical treatment, military affairs, chemical industry.But because the influence of the character of pitch own, the aperture of the asphalt-base globular active carbon that conventional steam activation makes belong to mostly range of micropores (＜20A), can obtain the mesopore about a small amount of 20-40A after the deep activation, but can not obtain more wide-aperture mesopore.This has just limited the range of application of asphalt-base globular active carbon, particularly the application aspect the absorption of liquid phase macromole.Therefore, press for and develop asphalt-base globular active carbon with flourishing central hole structure.
In order to improve the active of above-mentioned gac and to enlarge its range of application, people adopt the whole bag of tricks to increase its specific surface, particularly increase the mesopore (＞20A) ratio of structure.For example, the An Tianyuan of Japan and Yu Jing such as take charge of for a long time at the macromolecule complex that the scholar utilizes organo-metallic mixture or metal, have prepared the gac [Chem.Mater.1996,8,454-462 and TANSO (Japanese) 1996,175,243-248] of mesopore prosperity.Used organo-metallic mixture and metal macromolecule complex need oneself preparation in its technology, and its preparation method mainly contains following three kinds:
(1) contains the self-polymerization of metal composite (as 2,4-hexadiene base [iron tricarbonyl] vinylformic acid) of vinyl or the copolymerization of these metal composites and vinyl cyanide (AN), vinylbenzene (ST), methyl methylacrylic acid (MMA) or 4-ethylpyridine (VP).
(2) metallic compound and the organic macromolecule that contains certain functional group (as poly-propionitrile (PAN), poly-ethylpyridine (PVP) and contain-COO-,-NR 2Or cyclopentadienyl coordinate polystyrene (PST) etc.) the formation coordination compound.
(3) soluble metal organic macromolecule compound (as gathering ethyl dicyclopentadienyl iron, 1,1 '-two menaphthyl ferrocene etc.) mixes with pitch or organic polymer (as polyacrylonitrile (PAN), poly-ethylpyridine (PVP) etc.).
An Tianyuan and Yu Jing the scholar such as take charge of for a long time and adopt the third method more; Mid-temperature pitch (SP=85 ℃) is dissolved in tetrahydrofuran (THF) or the quinoline, then with organometallic compound (as Y (acac) 3, Ln (C 5H 5) 3(Ln=Y, La, Yb, Nd, Sm, Gd etc.), (C 5H 5) 2CO, (C 5H 5) 2YbCl, Fe (C 5H 5) 2Deng) mix, under vacuum state, remove tetrahydrofuran (THF) or quinoline then, the pitch of the containing metal particulate that makes like this mixes with hard pitch (SP=280 ℃) again, after the fragmentation again through the gac that does not melt, charing, activation can make the mesopore prosperity.The BET and the aperture structure of the gac that above method makes are as shown in table 1.
Table 1
Add metal BET specific surface area (m 2/g) Middle pore specific surface area (m 2/g) Mesopore ratio (%) Aperture ()
?Y(C 5H 5) 3 ????210 ????139 ????66.3 ????49.0
?Yb(C 5H 5) 3 ????261 ????193 ????74.1 ????56.8
?La(C 5H 5) 3 ????191 ????125 ????65.5 ????57.6
????YCl a ????237 ????40 ????16.9 ????33.8
The above results shows, although the mesopore ratio is higher, Zong because specific surface is few, the absolute value of mesopore specific surface is also little.Adopt organo-metallic mixture and the metal macromolecule complex that needs oneself to prepare in the technology, make the pitch of containing metal particulate with soft pitch after, also to increase and hard pitch blended step, not only make the preparation method complicated, also improved the cost of asphalt based active carbon greatly, it is unformed granular that the gained gac is, sphericity is poor, intensity difference in the use, resistance is big, and adsorption desorption speed is slow.
The objective of the invention is to develop the method that a kind of total specific surface height, mesopore specific surface height, method interpolation metal inorganic salt simple, with low cost prepare asphalt-base globular active carbon.
Preparation method of the present invention mixes general metal inorganic salt with hard pitch (SP=200-300 ℃) and organic solvent, the homodisperse pitch of preparation metal particle, utilize the bitumen ball of the bitumen production containing metal particulate of containing metal particulate then, at last, with above-mentioned bitumen ball through do not melt, charing and activation treatment get the product gac.
The used asphalt stock of the present invention is that the useless pitch of the by product in petroleum pitch, coal-tar pitch, pitch earth or the oil refining makes it the hard pitch that modification obtains through thermal treatment or oxide treatment.
The used metal inorganic salt of the present invention is the water soluble salt of transition metal or rare earth metal, as metal chloride, nitrate, vitriol, acetate etc.
The used organic solvent of the present invention is not only water-soluble but also organic solvent that can dissolved bitumen, as pyridine, quinoline, tetrahydrofuran (THF) etc.
The asphalt stock of containing metal particulate is made by following method:
At first metal inorganic salt is made into the aqueous solution, add organic solvent again, mix with pitch high temperature (100-300 ℃) in autoclave then, the ratio of pitch, inorganic salt and organic solvent is 1: (0.01-0.1): (0.1-0.5), the add-on of water with 20-100 ℃ can dissolve added inorganic salt degree of being, utilize the method for high temperature or vacuum extraction to remove at last and anhydrate and organic solvent.With the above-mentioned pitch that makes again with aromatic solvent (one or more of benzene,toluene,xylene, naphthalene, methylnaphthalene) with 1: (0.10-: the high temperature (100-300 ℃) in autoclave of ratio 0.50) mixes, and can make the material asphalt of the containing metal particulate that is suitable for preparing bitumen ball.The purpose that adds for the first time organic solvent is that particulate is mixed in pitch, and the purpose that adds aromatic solvent for the second time is to help preparing the porous asphalt ball.
The asphalt emulsification method balling-up that aforesaid method is made, the bitumen ball of preparation containing metal particulate, again through pre-treatment, do not melt, asphalt-base globular active carbon that charing and activation treatment can make the mesopore prosperity, existing division is as follows.
The pre-treatment of the bitumen ball of containing metal particulate before not melting: be immersed in and dissolve each other with aromatic solvent and do not have in the organic solvent (as catenaneses such as Fatty Alcohol(C12-C14 and C12-C18) such as methyl alcohol, ethanol or hexane, heptane, petroleum naphthas) of affinity with pitch or utilize vacuum extraction with adding bitumen ball that inorganic metal salt makes, extracting goes out the aromatic solvent in the bitumen ball, makes the porous asphalt ball of containing metal particulate.
The not melt processed of the bitumen ball of containing metal particulate: the porous asphalt ball of containing metal particulate carries out not melt processed under 200-350 ℃ temperature in oxidizing atmosphere.Used oxidizing gas can be air or oxygen, ozone etc. and the gas mixture of rare gas element.
The charing of not melting the bitumen ball of containing metal particulate is handled: the bitumen ball that does not melt the containing metal particulate rises to 700-1200 ℃ with the temperature rise rate of 5-20 ℃/min and carries out charing and handle under protection of inert gas.
The activation treatment of the charing bitumen ball of containing metal particulate: the charing bitumen ball of containing metal particulate utilizes water vapour or carbonic acid gas to carry out activation treatment under 700-1200 ℃, can make the asphalt-base globular active carbon of mesopore prosperity.
The present invention is described in detail by the following examples.
Embodiment 1
The preparation of nickeliferous asphalt stock
With 8.1 gram NiCl 26H 2O is dissolved in the 40ml water, is made into the aqueous solution, adds in the 200 gram pitches with the 100ml pyridine then, 170 ℃ of mixing and stirring, high temperature steams water and pyridine then in autoclave, adds 60 gram naphthalenes again, stir at 170 ℃, can obtain containing Ni after cooling, the fragmentation 2+The material asphalt that is suitable for preparing the porous asphalt ball.Prepare the bitumen ball of containing metal particulate by the method for above-mentioned emulsification balling-up, again through give processing, do not melt, charing and activation treatment can get asphalt-base globular active carbon.
Embodiment 2
The preparation of iron content asphalt stock
With 4 gram Fe (NO 3) 2Be dissolved in the 60ml water, be made into the aqueous solution, add the pitch of 200 grams then with the 150ml pyridine, in autoclave,, steam water and pyridine then, add 100 gram naphthalenes again, stir, can obtain containing Fe after cooling, the fragmentation at 140 ℃ 140 ℃ of mixing and stirring 2+The material asphalt that is suitable for preparing the porous asphalt ball.Other are with embodiment 1.
Embodiment 3
Contain the preparation of gadolinium asphalt stock
With 8 gram Y (NO 3) 36H 2O is dissolved in the 100ml water, is made into the aqueous solution, adds 200 gram pitches with the 200ml pyridine then, 140 ℃ of mixing and stirring, steams water and pyridine then in autoclave, adds 100 gram naphthalenes again, stirs at 140 ℃, can obtain containing Y after cooling, the fragmentation 3+The material asphalt that is suitable for preparing the porous asphalt ball.Other is with embodiment 1.
The results are shown in following table 2 and accompanying drawing.
Add metal BET specific surface area (m2/g) Middle pore specific surface area (m2/g) Total pore volume (cm3/g) Mesopore ratio * (%) Mean pore size * * (A)
?NiCl 2·6H 2O ????1297 ????188 ????0.80 ????28 ????63
?Fe(NO 3) 2 ????1270 ????268 ????87 ????54 ????62
?Y(NO a) 3·6H 2O ????1120 ????136 ????0.72 ????40 ????75
*: the mesopore ratio is drawn than total pore volume by mesopore volume;
*: mean pore size is drawn from desorption branch (4V/ ) by the BJH method.
The above results shows:
1. total specific surface is up to 1120-1297m 2/ g, the mesopore specific surface is up to 136-268m 2/ g wherein not only contains the mesopore of 20-40 , but also contains the mesopore of 300-500 , and average hole is 62-75 .Therefore, this gac is not only active high, and applied range.
2. increase the balling-up of bituminous emulsion process in the method, gained gac sphericity height, intensity height in therefore using, resistance is little, and adsorption desorption is fast.

Claims (5)

1. method for preparing the asphalt-base globular active carbon of mesopore prosperity, its feature is as follows: at first inorganic salt are made into the aqueous solution, add the organic solvent that dissolves each other with water and can dissolved bitumen again, mix with pitch high temperature (100-300 ℃) in autoclave then, the ratio of pitch, inorganic salt and organic solvent is 1: (0.01-0.1): (0.1-0.5), the add-on of water with 20-200 ℃ can dissolve added inorganic salt degree of being, utilize the method for high temperature or vacuum extraction to remove at last and anhydrate and organic solvent.With the above-mentioned pitch that makes again with aromatic solvent with 1: the high temperature (100-300 ℃) in autoclave of ratio (0.1-0.5) mixes, can make the material asphalt of the containing metal particulate that is suitable for preparing bitumen ball, after the emulsion process balling-up, again through do not melt, charing, activation treatment can get the asphalt-base globular active carbon of mesopore prosperity.
2. the method for claim 1 is characterized in that used inorganic salt are the salt of filtering metal or rare earth metal, as metal chloride, nitrate, vitriol and acetate etc.
3. the method for claim 1, the add-on that it is characterized in that water with 20-100 ℃ can dissolve added inorganic salt degree of being.
4. as claim 1,2 or 3 described methods, it is characterized in that used organic solvent for can be water-soluble can dissolved bitumen organic solvent.
5. method as claimed in claim 4 is characterized in that used organic solvent preferably selects pyridine or quinoline for use.
CN98104731A 1998-01-23 1998-01-23 Method for preparing asphalt based spherical active carbon by adding inorganic metal salt Expired - Fee Related CN1089097C (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6843835B2 (en) 2001-03-27 2005-01-18 The Procter & Gamble Company Air cleaning apparatus and method for cleaning air
CN105271225A (en) * 2015-11-05 2016-01-27 新奥科技发展有限公司 Preparing method for activated carbon
CN105983389A (en) * 2016-07-15 2016-10-05 宋玉琴 Preparation method of lanthanum-containing activated carbon
CN107720747A (en) * 2017-10-31 2018-02-23 中国科学院山西煤炭化学研究所 A kind of preparation method rich in mesopore asphalt-base globular active carbon
CN107880572A (en) * 2017-11-17 2018-04-06 山西大学 A kind of preparation method of nano transition metal particle doping pitch
CN108190853A (en) * 2018-01-18 2018-06-22 中国科学院山西煤炭化学研究所 A kind of preparation method of reticulated foams wall hollow carbon sphere
CN108516547A (en) * 2018-05-16 2018-09-11 辽宁科技大学 The preparation method of carbon black-coal tar pitch complex spherical activated carbon
CN108786733A (en) * 2018-06-20 2018-11-13 湘潭大学 A kind of micro-meter scale receives hole charcoal ball CO2The preparation method of adsorbent
CN109052397A (en) * 2018-09-25 2018-12-21 湖南曦威新材料有限公司 A kind of preparation method with hierarchical pore structure asphalt-base spherical activated carbon

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3917806A (en) * 1973-09-27 1975-11-04 Kureha Chemical Ind Co Ltd Method for the preparation of carbon moldings and activated carbon molding therefrom
JPS6114110A (en) * 1984-06-26 1986-01-22 Kawasaki Steel Corp Manufacture of fine and hollow body of carbon
CN1036333C (en) * 1993-12-21 1997-11-05 中国石油化工总公司石油化工科学研究院 Method for preparation of active carbon

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7147692B2 (en) 2001-03-27 2006-12-12 The Procter & Gamble Company Air cleaning apparatus and method for cleaning air
US6843835B2 (en) 2001-03-27 2005-01-18 The Procter & Gamble Company Air cleaning apparatus and method for cleaning air
CN105271225A (en) * 2015-11-05 2016-01-27 新奥科技发展有限公司 Preparing method for activated carbon
CN105983389B (en) * 2016-07-15 2018-11-13 宋玉琴 The preparation method of activated carbon containing lanthanum
CN105983389A (en) * 2016-07-15 2016-10-05 宋玉琴 Preparation method of lanthanum-containing activated carbon
CN107720747A (en) * 2017-10-31 2018-02-23 中国科学院山西煤炭化学研究所 A kind of preparation method rich in mesopore asphalt-base globular active carbon
CN107720747B (en) * 2017-10-31 2020-02-14 中国科学院山西煤炭化学研究所 Preparation method of mesoporous-asphalt-based spherical activated carbon
CN107880572A (en) * 2017-11-17 2018-04-06 山西大学 A kind of preparation method of nano transition metal particle doping pitch
CN108190853A (en) * 2018-01-18 2018-06-22 中国科学院山西煤炭化学研究所 A kind of preparation method of reticulated foams wall hollow carbon sphere
CN108516547A (en) * 2018-05-16 2018-09-11 辽宁科技大学 The preparation method of carbon black-coal tar pitch complex spherical activated carbon
CN108786733A (en) * 2018-06-20 2018-11-13 湘潭大学 A kind of micro-meter scale receives hole charcoal ball CO2The preparation method of adsorbent
CN109052397A (en) * 2018-09-25 2018-12-21 湖南曦威新材料有限公司 A kind of preparation method with hierarchical pore structure asphalt-base spherical activated carbon
CN109052397B (en) * 2018-09-25 2021-12-03 湖南曦威新材料有限公司 Preparation method of asphalt-based spherical activated carbon with hierarchical pore structure

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