CN103880006A - Method for preparing large particle size phenolic resin spherical activated carbon - Google Patents
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- CN103880006A CN103880006A CN201410093429.XA CN201410093429A CN103880006A CN 103880006 A CN103880006 A CN 103880006A CN 201410093429 A CN201410093429 A CN 201410093429A CN 103880006 A CN103880006 A CN 103880006A
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Abstract
The invention relates to a method for preparing large particle size phenolic resin spherical activated carbon. The method comprises the following steps: dispersing hollow spheres with the particle size of 10-50nm into a thermoset phenolic resin at the room temperature, performing ultrasonic dispersion in ultrasonic wave, wherein the mass ratio of the thermoset phenolic resin to the hollow spheres is 100:(5-12), and the hollow spheres are one or combination of any two of starch based hollow spheres, phenolic resin based hollow spheres, polystyrene-based hollow spheres and polyurethane-based hollow spheres; putting the mixture into a hollow spherical polyethylene shell with the diameter of 1.5-6cm; subsequently curing to form in an oven; removing the polyethylene shell; subsequently heating a cured phenolic resin ball to be 800-1000 DEG C in a high temperature carbonization activating furnace; preserving heat for 0.5-2 hours; and naturally cooling to obtain the spherical activated carbon. The method provided by the invention has the advantages that the process is simple, the raw materials are nearly non-toxic, the yield is high, and the like. The prepared spherical activated carbon has the advantages of smooth surface, high spherical degree, large particle size, high strength, high specific surface area and the like.
Description
Technical field
The present invention relates to the preparation method of the alkyd resin based spheric active carbon of a kind of large particle diameter.
Background technology
Spheric active carbon, owing to having abundant pore structure, good sphericity, higher physical strength and acid and alkali-resistance and a series of good characteristics such as high temperature resistant, can be widely used in the fields such as environmental protection, chemical defence, gas delivery and solvent recuperation.
Prepare at present spheric active carbon and mainly adopt suspension polymerization, as having reported, patent CN101157451 and CN101348573 the preparation method of alkyd resin based spheric active carbon linear phenolic resin, alcohol, hexamethylenetetramine are made to spheric active carbon through suspension polymerization in dispersion liquid.But suspension polymerization can only be prepared the spheric active carbon of the following particle diameter of grade conventionally, this cause because resistance is excessive in some large-scale an adsorption devices compared with the spherical carbon of small particle size its be difficult to application.Adopt mechanical rolling method can prepare the spheric active carbon of centimetre-sized, as patent CN102259853A has reported the preparation method of ball shape active carbon, by after powdered carbon and coal-tar pitch mixing, through bowl granulator pelletizing, but the spheric active carbon of preparation exists, and surface irregularity, sphericity are poor, intensity and the defect such as specific surface area is low, undesirable in actual applications.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of sphere diameter at 1cm-5cm, sphericity is 95%-98%, intensity is 93%-97%, specific surface area 800-1200m
2the preparation method of the alkyd resin based spheric active carbon of/g.
Realize technical scheme of the present invention as follows:
A preparation method for the alkyd resin based spheric active carbon of large particle diameter, comprises the steps:
(1) hollow ball that is 10-50nm by particle diameter under room temperature is scattered in heat-reactive phenolic resin, and in ultrasonic wave, carry out ultrasonic dispersion, wherein, heat-reactive phenolic resin: the mass ratio of hollow ball is: 100:5-12, described hollow ball is the wherein a kind of or combination of any two kinds of starch base hollow ball, alkyd resin based hollow ball, polystyrene-based hollow ball, polyurethane-base hollow ball;
(2) mixture in step (1) is inserted in the hollow ball-shape polyethylene shell that diameter is 1.5cm-6cm to then curing molding in baking oven;
(3) remove after polyethylene shell, curing phenolic resin balls is heated in high temperature carbonization activation furnace after 800-1000 DEG C, constant temperature 0.5h-2h, obtains spheric active carbon after naturally cooling.
In above-mentioned steps (2), in baking oven, curing molding is: at 60-70 DEG C of curing 0.5-1h, be then warming up to 90-100 DEG C of curing 0.5-1h, finally at 160-180 DEG C of curing 1-2h.
In described step (3), the flow rates activation spherical carbon in constant temperature zone process with 0.3-5ml/min.
Phenolic resin balls curing in described step (3) is heated to 800-1000 DEG C with the temperature rise rate of 0.5-3 DEG C/min in high temperature carbonization activation furnace.
Ultrasonic echography jitter time in described step (1): 20min-60min.
Described heat-reactive phenolic resin is at room temperature in a liquid state, and viscosity is 800-1200Pas.
The sphere diameter of described spheric active carbon is regulated and controled by the diameter of hollow ball-shape polyethylene shell.
Balling-up mechanism of the present invention is: nano level hollow ball evenly spread in heat-reactive phenolic resin, is then injected in hollow ball-shape polyethylene shell, and curing molding at a certain temperature, last carbonization-activation makes spheric active carbon.The hole that this preparation method utilizes hollow ball to produce on the one hand avoids resol charing process because a large amount of light constituent volatilizations causes breaking of charcoal ball; On the other hand for steam activation spherical carbon provides favourable water vapour admission passage.Present method operational path is simple, the almost non-toxic property of raw material, productive rate are high; And tool of the present invention has the following advantages: spheric active carbon prepared by present method has smooth surface, sphericity high (95%-98%), sphere diameter large (1cm-5cm), the high (800-1200m of specific surface area
2/ g), the advantage such as intensity high (93%-97%), the diameter that can change as requested hollow ball-shape polyethylene shell simultaneously regulates and controls to prepare the diameter of spherical carbon.
Embodiment
Embodiment 1:
The starch base hollow ball that is 10nm by 0.5g particle diameter under room temperature is scattered in the heat-reactive phenolic resin that 10g viscosity is 800Pas, ultrasonic 20min in ultrasonic wave.Above mixture is inserted in the hollow ball-shape polyethylene shell that diameter is 1.5cm, then curing molding in baking oven, the curing molding is here: first at 70 DEG C of curing 0.5h, be then warming up to 90 DEG C of curing 0.5h, finally at 160 DEG C of curing 2h; Remove after polyethylene shell, curing phenolic resin balls is heated to after 800 DEG C in high temperature carbonization activation furnace to constant temperature 0.5h with the temperature rise rate of 0.5 DEG C/min.Flow rates activation spherical carbon in constant temperature zone process with 0.3ml/min, obtains spheric active carbon, the sphericity of the spheric active carbon of preparing after naturally cooling: 98%, and sphere diameter: 1cm, intensity: 97%, specific surface area: 800m
2/ g.
Embodiment 2:
The alkyd resin based hollow ball that is 20nm by 0.7g particle diameter under room temperature is scattered in the heat-reactive phenolic resin that 10g viscosity is 1000Pas, ultrasonic 50min in ultrasonic wave; Above mixture is inserted in the hollow ball-shape polyethylene shell that diameter is 2.0cm, then curing molding in baking oven, the curing molding is here: first at 60 DEG C of curing 1h, be then warming up to 95 DEG C of curing 0.5h, finally at 160 DEG C of curing 1h.Remove after polyethylene shell, curing phenolic resin balls is heated to after 850 DEG C in high temperature carbonization activation furnace to constant temperature 0.5h with the temperature rise rate of 1 DEG C/min.Flow rates activation spherical carbon in constant temperature zone process with 0.5ml/min, obtains spheric active carbon, the sphericity of the spheric active carbon of preparing after naturally cooling: 98%, and sphere diameter: 1.4cm, intensity: 97%, specific surface area: 840m
2/ g.
Embodiment 3:
The polystyrene-based hollow ball that is 30nm by 0.9g particle diameter under room temperature is scattered in the heat-reactive phenolic resin that 10g viscosity is 1200Pas, ultrasonic 30min in ultrasonic wave.Above mixture is inserted in the hollow ball-shape polyethylene shell that diameter is 2.5cm, then curing molding in baking oven, the curing molding is here: first at 65 DEG C of curing 0.5h, be then warming up to 90 DEG C of curing 1h, finally at 160 DEG C of curing 0.5h.Remove after polyethylene shell, curing phenolic resin balls is heated to after 900 DEG C in high temperature carbonization activation furnace to constant temperature 1h with the temperature rise rate of 1.5 DEG C/min.Flow rates activation spherical carbon in constant temperature zone process with 1.0ml/min, obtains spheric active carbon, the sphericity of the spheric active carbon of preparing after naturally cooling: 97%, and sphere diameter: 1.9cm, intensity: 96%, specific surface area: 890m
2/ g.
Embodiment 4:
The polyurethane-base hollow ball that is 40nm by 1.1g particle diameter under room temperature is scattered in the heat-reactive phenolic resin that 10g viscosity is 1200Pas, ultrasonic 60min in ultrasonic wave.Above mixture is inserted in the hollow ball-shape polyethylene shell that diameter is 3.0cm to then curing molding in baking oven, the curing molding here: first at 70 DEG C of curing 1h, be then warming up to 100 DEG C of curing 0.5h, finally at 170 DEG C of curing 2h.Remove after polyethylene shell, curing phenolic resin balls is heated to after 950 DEG C in high temperature carbonization activation furnace to constant temperature 1h with the temperature rise rate of 2.0 DEG C/min.Flow rates activation spherical carbon in constant temperature zone process with 2.0ml/min, obtains spheric active carbon, the sphericity of the spheric active carbon of preparing after naturally cooling: 97%, and sphere diameter: 2.5cm, intensity: 96%, specific surface area: 930m
2/ g.
Embodiment 5:
The resol that is 50nm by 1.2g particle diameter under room temperature and polystyrene-based hollow ball are scattered in the heat-reactive phenolic resin that 10g viscosity is 900Pas, wherein, alkyd resin based hollow ball and polystyrene-based hollow ball mass ratio are 1:2, ultrasonic 40min in ultrasonic wave.Above mixture is inserted in the hollow ball-shape polyethylene shell that diameter is 3.5cm to then curing molding in baking oven, the curing molding here: first at 70 DEG C of curing 0.5h, be then warming up to 100 DEG C of curing 1h, finally at 170 DEG C of curing 1h.Remove after polyethylene shell, curing phenolic resin balls is heated to after 1000 DEG C in high temperature carbonization activation furnace to constant temperature 1.5h with the temperature rise rate of 2.5 DEG C/min.Flow rates activation spherical carbon in constant temperature zone process with 3.0ml/min, obtains spheric active carbon, the sphericity of the spheric active carbon of preparing after naturally cooling: 96%, and sphere diameter: 2.8cm, intensity: 95%, specific surface area: 970m
2/ g.
Embodiment 6:
The starch that is 30nm by 1.0g particle diameter under room temperature and polyurethane-base hollow ball are scattered in the heat-reactive phenolic resin that 10g viscosity is 800Pas, and wherein, starch base hollow ball and polyurethane-base hollow ball mass ratio are 2:1, ultrasonic 60min in ultrasonic wave.Above mixture is inserted in the hollow ball-shape polyethylene shell that diameter is 4.5cm to then curing molding in baking oven, the curing molding here: first at 60 DEG C of curing 0.5h, be then warming up to 95 DEG C of curing 0.5h, finally at 175 DEG C of curing 2h.Remove after polyethylene shell, curing phenolic resin balls is heated to after 800 DEG C in high temperature carbonization activation furnace to constant temperature 1.5h with the temperature rise rate of 3.0 DEG C/min.Flow rates activation spherical carbon in constant temperature zone process with 3.5ml/min, obtains spheric active carbon, the sphericity of the spheric active carbon of preparing after naturally cooling: 96%, and sphere diameter: 4.0cm, intensity: 94%, specific surface area: 1050m
2/ g.
Embodiment 7:
The starch that is 20nm by 0.8g particle diameter under room temperature and alkyd resin based hollow ball are scattered in the heat-reactive phenolic resin that 10g viscosity is 1100Pas, and wherein, starch base hollow ball and alkyd resin based hollow ball mass ratio are 1:1, ultrasonic 40min in ultrasonic wave.Above mixture is inserted in the hollow ball-shape polyethylene shell that diameter is 5.0cm to then curing molding in baking oven, curing molding: first at 65 DEG C of curing 0.5h, be then warming up to 95 DEG C of curing 1h, finally at 180 DEG C of curing 2h.Remove after polyethylene shell, curing phenolic resin balls is heated to after 900 DEG C in high temperature carbonization activation furnace to constant temperature 2.0h with the temperature rise rate of 0.5 DEG C/min.Flow rates activation spherical carbon in constant temperature zone process with 4.0ml/min, obtains spheric active carbon, the sphericity of the spheric active carbon of preparing after naturally cooling: 95%, and sphere diameter: 4.3cm, intensity: 93%, specific surface area: 1120m
2/ g.
Embodiment 8:
The resol that is 10nm by 0.6g particle diameter under room temperature and polyurethane-base hollow ball are scattered in the heat-reactive phenolic resin that 10g viscosity is 1200Pas, and wherein, alkyd resin based hollow ball and polyurethane-base hollow ball mass ratio are 3:1, ultrasonic 60min in ultrasonic wave.Above mixture is inserted in the hollow ball-shape polyethylene shell that diameter is 6.0cm to then curing molding in baking oven, the curing molding here: first at 70 DEG C of curing 1h, be then warming up to 90 DEG C of curing 0.5h, finally at 180 DEG C of curing 1h.Remove after polyethylene shell, curing phenolic resin balls is heated to after 1000 DEG C in high temperature carbonization activation furnace to constant temperature 2.0h with the temperature rise rate of 1.0 DEG C/min.Flow rates activation spherical carbon in constant temperature zone process with 5.0ml/min, obtains spheric active carbon, the sphericity of the spheric active carbon of preparing after naturally cooling: 95%, and sphere diameter: 5.0cm, intensity: 93%, specific surface area: 1200m
2/ g.
Claims (7)
1. a preparation method for the alkyd resin based spheric active carbon of large particle diameter, is characterized in that, comprises the steps:
(1) hollow ball that is 10-50nm by particle diameter under room temperature is scattered in heat-reactive phenolic resin, and in ultrasonic wave, carry out ultrasonic dispersion, wherein, heat-reactive phenolic resin: the mass ratio of hollow ball is: 100:5-12, described hollow ball is the wherein a kind of or combination of any two kinds of starch base hollow ball, alkyd resin based hollow ball, polystyrene-based hollow ball, polyurethane-base hollow ball;
(2) mixture in step (1) is inserted in the hollow ball-shape polyethylene shell that diameter is 1.5cm-6cm to then curing molding in baking oven;
(3) remove after polyethylene shell, curing phenolic resin balls is heated in high temperature carbonization activation furnace after 800-1000 DEG C, constant temperature 0.5h-2h, obtains spheric active carbon after naturally cooling.
2. the preparation method of the alkyd resin based spheric active carbon of a kind of large particle diameter according to claim 1, it is characterized in that, in above-mentioned steps (2), in baking oven, curing molding is: at 60-70 DEG C of curing 0.5-1h, then be warming up to 90-100 DEG C of curing 0.5-1h, finally at 160-180 DEG C of curing 1-2h.
3. the preparation method of the alkyd resin based spheric active carbon of a kind of large particle diameter according to claim 1, is characterized in that, in described step (3), and the flow rates activation spherical carbon in constant temperature zone process with 0.3-5ml/min.
4. the preparation method of the alkyd resin based spheric active carbon of a kind of large particle diameter according to claim 1, it is characterized in that, phenolic resin balls curing in described step (3) is heated to 800-1000 DEG C with the temperature rise rate of 0.5-3 DEG C/min in high temperature carbonization activation furnace.
5. the preparation method of the alkyd resin based spheric active carbon of a kind of large particle diameter according to claim 1, is characterized in that, the ultrasonic echography jitter time in described step (1): 20min-60min.
6. according to the preparation method of the alkyd resin based spheric active carbon of a kind of large particle diameter described in any one in claim 1-5, it is characterized in that, described heat-reactive phenolic resin is at room temperature in a liquid state, and viscosity is 800-1200Pas.
7. according to the preparation method of the alkyd resin based spheric active carbon of a kind of large particle diameter described in any one in claim 1-5, it is characterized in that, the sphere diameter of described spheric active carbon is regulated and controled by the diameter of hollow ball-shape polyethylene shell.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058401A (en) * | 2014-07-11 | 2014-09-24 | 北京科技大学 | Preparation method of porous carbon microspheres |
| CN104986764A (en) * | 2015-07-13 | 2015-10-21 | 安徽成方新材料科技有限公司 | Green environment-friendly light-weight porous reinforced compound spherical active carbon and preparation method of active carbon |
| CN105293489A (en) * | 2015-11-16 | 2016-02-03 | 昆明理工大学 | Regeneration method of waste active carbon for monosodium glutamate by supersonic wave and spray |
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| CN105293489A (en) * | 2015-11-16 | 2016-02-03 | 昆明理工大学 | Regeneration method of waste active carbon for monosodium glutamate by supersonic wave and spray |
| CN105293489B (en) * | 2015-11-16 | 2018-03-06 | 昆明理工大学 | A kind of method of ultrasonic atomization regenerating waste monosodium glutamate activated carbon |
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