CN1986401A - Improved process for preparing porous microsphere active carbon - Google Patents
Improved process for preparing porous microsphere active carbon Download PDFInfo
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- CN1986401A CN1986401A CN 200710000074 CN200710000074A CN1986401A CN 1986401 A CN1986401 A CN 1986401A CN 200710000074 CN200710000074 CN 200710000074 CN 200710000074 A CN200710000074 A CN 200710000074A CN 1986401 A CN1986401 A CN 1986401A
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Abstract
The improved process for preparing high strength porous microsphere active carbon includes the following steps: oxidizing thermosetting resin ball at 60-400 deg.c in oxygen containing atmosphere or pre-treating thermosetting resin ball at 60-300 deg.c in oxidizing acid, SO2 or SO3; carbonizing at 600-1200 deg.c in helium, nitrogen or their mixture atmosphere; and activating at 600-1200 deg.c in activating water vapor atmosphere to obtain high strength porous microsphere active carbon with grain size of 10 micron to 2 mm, BET specific surface area of 500-4000 sq m/g, and grain strength of 50-200 MPa. The process is simple, low in cost and high in yield, and the prepared microsphere active carbon has high strength and high purity and is one excellent medical active adsorption material.
Description
Technical field
The present invention relates to a kind of high intensity, porous microsphere active carbon, specifically relate to a kind of superstrength porous microsphere active carbon of the preparation of improving one's methods.
Background technology
Gac is excellent sorbing material, according to the difference of shape, can be divided into Powdered Activated Carbon, granular carbon, fibrous activated carbon and ball shape active carbon etc.Activated carbon fiber directly is opened on fiber surface based on micropore and micropore, so adsorption desorption speed is fast, loading capacity is big.The pore structure of granular carbon, Powdered Activated Carbon is relatively disperseed, and absorption property is good not as activated carbon fiber, but its cost is low.Advantages such as ball shape active carbon smooth surface, shape is regular, physical strength is high, particle diameter is controlled, good flowability is arranged, the convection cell resistance is little make activated carbon microballon be widely used in blood perfusion, lithium ion battery negative material, super capacitor anode material, chromatographic column filler, support of the catalyst and are used for the treatment of the sorbing material of chronic renal failure.
Because activated carbon microballon has a series of advantage, in recent years, has caused experts and scholars' extensive concern about the research of microsphere active carbon.Patent CN1075539C has reported a kind of technology for preparing phenolic resin base globe activated char, with linear phenolic resin with after solidifying agent mixes, make block mixture,, obtain the phenolic resin base globe activated char of particle diameter about 2mm through fragmentation, emulsification balling-up, charing and activating process.
A kind of novel process of expanded phenol-formaldehyde resin based carbon microsphere preparation has been reported in patent application 200410016702.5, it is aqueous solution with the ethanolic soln and the tensio-active agent of linear phenolic resin, form uniform milk sap, then under 100 ℃～150 ℃ temperature, stir and solidify, the temperature rise rate with 5 ℃～10 ℃/min is heated to 800 ℃～1200 ℃ again, and constant temperature carried out charing in 0.5～5 hour, after the cooling, just obtain said resol based carbon microsphere.
Patent application 200510000055.3 has reported that the polymer microsphere resin with the halogen-containing element of 100nm～100 μ m is a raw material, through alkaline purification, oxide treatment, obtaining the polymer-based carbon carbon microspheres of particle size range at 100nm～100 μ m through charing, graphitization processing.
The method for preparing the mesophase pitch carbon microspheres has been reported in patent CN1057319C, CN1100093C, CN1116386C, CN1151060C, patent application 200310122155.4 and patent application 200510045481.9.
United States Patent (USP) Re29,101 and the special public clear 62-11611 of Japanese Patent reported a kind of method for preparing the asphalt based active carbon microballoon.Petroleum pitch or coal-tar pitch are mixed with a kind of pore-forming material, with mixture balling-up in a kind of surfactant soln, obtain the bitumen ball of certain particle diameter, utilize a kind of solvent with the tensio-active agent extracting in the bitumen ball subsequently, obtain the porous asphalt ball, again the oxidation of porous asphalt ball is not melted with carbonization-activation after just obtain the asphalt based active carbon microballoon.
The method complicated process of preparation of prior art for preparing ball shape active carbon, the ball shape active carbon intensity that makes is low, is difficult for realizing suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of superstrength porous microsphere active carbon that utilizes the inventive method preparation.
A further object of the present invention provides a kind of method for preparing the superstrength porous microsphere active carbon.
The superstrength porous microsphere active carbon of preparation as follows provided by the invention, said method comprises: be in the atmosphere of 1～50 volume % with commercially available thermosetting resin ball in oxygen level (a), oxidation is 1～10 hour under 60 ℃～400 ℃ temperature, or with commercially available thermosetting resin under 60 ℃～300 ℃, the acid or the SO that have oxidisability at the vitriol oil, chloric acid, perchloric acid or oleum etc.
2, SO
3Carry out pre-treatment in the atmosphere of gas, handled 1～15 hour; (b) with above-mentioned pretreated material in such as helium, nitrogen or its mixed inert atmosphere gas, under 600 ℃～1200 ℃, carry out carbonizing treatment; (c) under 600 ℃～1200 ℃, under steam activation atmosphere, carry out activation treatment 10min～3 hour, obtain the porous microsphere active carbon that single particle intensity is 50～200Mpa.
Superstrength porous microsphere active carbon according to following preferred method preparation provided by the invention, said method comprises: be in the atmosphere of 5～40 volume % with commercially available thermosetting resin ball in oxygen level (a), oxidation is 1～10 hour under 80 ℃～300 ℃ temperature, or with commercially available thermosetting resin under 100 ℃～200 ℃, the acid or the SO that have oxidisability at the vitriol oil, chloric acid, perchloric acid or oleum etc.
2, SO
3Carry out pre-treatment 2～10 hours in the atmosphere of gas; (b) with above-mentioned pretreated material in such as helium, nitrogen or its mixed inert atmosphere gas, under 700 ℃～1100 ℃, carry out carbonizing treatment; (c) under 700 ℃～1100 ℃, under steam activation atmosphere, carry out activation treatment 10min～3 hour, obtain the porous microsphere active carbon that single particle intensity is 60-200Mpa.
Superstrength porous microsphere active carbon according to following more preferably method preparation provided by the invention, said method comprises: be in the atmosphere of 10～35 volume % with commercially available thermosetting resin ball in oxygen level (a), oxidation is 5～8 hours under 150 ℃～200 ℃ temperature, or with commercially available thermosetting resin under 150 ℃～200 ℃, the acid or the SO that have oxidisability at the vitriol oil, chloric acid, perchloric acid or oleum etc.
2, SO
3Carry out pre-treatment 3～10 hours in the atmosphere of gas; (b) with above-mentioned pretreated material in such as helium, nitrogen or its mixed inert atmosphere gas, under 900 ℃～1000 ℃, carry out carbonizing treatment; (c) under 800 ℃～1000 ℃, under steam activation atmosphere, carried out activation treatment 20 minutes～2 hours, obtain the porous microsphere active carbon that single particle intensity is 100～190Mpa.
The particle diameter of gained porous microsphere active carbon is preferably 10 μ m-2mm, and BET method specific surface area is 500-4000m
2/ g; The particle diameter of gained porous microsphere active carbon more preferably is 10 μ m-2mm, and BET method specific surface area is 800-4000m
2/ g.The particle diameter of gained porous microsphere active carbon most preferably is 10 μ m-1mm, and BET method specific surface area is 1000-4000m
2/ g.
Advantage such as method technology provided by the invention is simple, preparation cost is low, yield is high, product intensity height, purity height and raw material sources are wide easily realizes mass preparation.
The porous microsphere active carbon that makes is wear-resistant, corrosion-resistant, increase the service life; Can use repeatedly, repeatedly regenerate, reduce use cost; And, still can keep good sphere, physical and mechanical properties and absorption property through after repeatedly regenerating.Good fluidity, foreign matter content is few, no crushed particles, purity is good.Ball shape active carbon is a kind of good medicinal active sorbing material, can be used in the active ingredient of blood purification, oral sorbing material and medicine.For example: it is low that the ball shape active carbon that hardness is high can make full use of its foreign matter content as blood purification with material, physical strength height, smooth surface and inclusion-free small-particle advantage such as come off.
Said commercially available thermosetting resin ball among the present invention, just like: phenolic resin balls, for example: phenolic varnish type phenol resins, fusible type phenol resins, phenolic varnish type alkyl phenol resin or fusible type alkyl phenol resin; Phenylethylene resin series ball, acrylic resin balls, acrylic resin ball, metha crylic resin balls, polyvinylidene chloride resin ball, furane resin ball, urea resin ball, melamine resin ball or Resins, epoxy ball.Preferred commercial phenolic resin ball and phenylethylene resin series ball.
The mensuration of specific surface area adopts the AsAp2020 of U.S. Merck ﹠ Co., Inc, thermal treatment temp: 350 ℃, and 6 hours; Analyze: the full hole of liquid nitrogen is analyzed.Utilize BET formula to calculate its specific surface area.
The mensuration of intensity adopts the granule strength determinator.
Description of drawings:
Accompanying drawing 1: the optical microscope photograph (* 30 times) of phenolic resin balls that is the source commodityization of embodiment 1.
Accompanying drawing 2: the optical microscope photograph (* 30 times) that is the porous microsphere active carbon of embodiment 1 preparation.
Accompanying drawing 3: the optical microscope photograph (* 10 times) of acrylic resin ball that is the source commodityization of embodiment 2.
Accompanying drawing 4: the optical microscope photograph (* 10 times) that is the porous microsphere active carbon of embodiment 2 preparations.
Accompanying drawing 5: the optical microscope photograph (* 20 times) of methacrylic resin ball that is the source commodityization of embodiment 3.
Accompanying drawing 6: the optical microscope photograph (* 20 times) that is the porous microsphere active carbon of embodiment 3 preparations.
Accompanying drawing 7: the electron scanning micrograph that is the commercial styrene resin balls of embodiment 4.
Accompanying drawing 8: the electron scanning micrograph that is the porous microsphere active carbon of embodiment 4 preparations.
Accompanying drawing 9: the electron scanning micrograph that is the porous microsphere active carbon of embodiment 5 preparations.
Accompanying drawing 10: the electron scanning micrograph that is the porous microsphere active carbon of embodiment 6 preparations.
Accompanying drawing 11: the electron scanning micrograph that is the porous microsphere active carbon of embodiment 7 preparations.
Accompanying drawing 12: the electron scanning micrograph that is the porous microsphere active carbon of embodiment 8 preparations.
Accompanying drawing 13: the electron scanning micrograph that is the porous microsphere active carbon of Comparative Examples 1 preparation.
Accompanying drawing 14: the electron scanning micrograph that is the porous microsphere active carbon of Comparative Examples 2 preparations.
Table 1 is that the individual seed strength of the porous microsphere active carbon of embodiment 1～8 and Comparative Examples 1 and 2 preparations compares.
Embodiment
Embodiment 1
With the heat-reactive phenolic resin ball of 300g, be oxidation 10 hours under 80 ℃ temperature in the atmosphere of 40 volume % in oxygen level.The product that obtains more than inciting somebody to action subsequently is elevated to 800 ℃ with 1 ℃/minute temperature rise rate in inert atmosphere nitrogen, and stops 2 hours under this temperature, carries out charing and handles.Subsequently, under 800 ℃, carry out activation treatment in the activation phenomenon of water vapour, soak time is 0.5 hour, promptly obtains the superstrength porous microsphere active carbon.The intensity of gained gac is listed in the table below in 1.
Embodiment 2
With the thermosetting acrylic resin ball of 200g, be oxidation 4 hours under 150 ℃ temperature in the atmosphere of 30 volume % in oxygen level.The above product that obtains in inert atmosphere nitrogen, is elevated to 600 ℃ with 1 ℃/minute temperature rise rate, and under this temperature, stopped 3 hours, carry out charing and handle.Subsequently, under 600 ℃, carry out activation treatment under the activation phenomenon of water vapour, soak time is 1 hour, promptly obtains the superstrength porous microsphere active carbon.Gained gac intensity is listed in the table below in 1.
Embodiment 3
With the thermoset methacrylic resin ball of 300g, under 80 ℃, utilized vitriol oil oxidation 10 hours.After 120 ℃ of oven dry, the above product that obtains in inert atmosphere nitrogen, is elevated to 1000 ℃ with the temperature rise rate of 3 ℃/min, and under this temperature, stopped 1 hour, carry out charing and handle.Subsequently, under 1000 ℃, carry out activation treatment under the activation phenomenon of water vapour, soak time is 0.5 hour, promptly obtains the superstrength porous microsphere active carbon.Gained gac intensity is listed in the table below in 1.
Embodiment 4
With thermosetting styrene and the divinyl benzene copolymer resin balls of 500g, under 300 ℃, utilized vitriol oil oxidation 8 hours.The above product that obtains in inert atmosphere nitrogen, is elevated to 1000 ℃ with 3 ℃/minute temperature rise rates, and under this temperature, stopped 2 hours, carry out charing and handle.Subsequently, under 900 ℃, carry out activation treatment under the activation phenomenon of water vapour, soak time is 0.5 hour, promptly obtains the superstrength porous microsphere active carbon.Gained gac intensity is listed in the table below in 1.
Embodiment 5
Thermoset polyvinylidene dichloride resin balls with 200g, in oxygen level is in the atmosphere of 10 volume %, oxidation is 2 hours under 400 ℃ temperature, with the above product that obtains in the inert atmosphere helium, be elevated to 1200 ℃ with 5 ℃/minute temperature rise rates, and under this temperature constant temperature 1 hour, carry out charing and handle.Subsequently, under 1000 ℃, carry out activation treatment under the activation phenomenon of water vapour, soak time is 1 hour, promptly obtains the superstrength porous microsphere active carbon.Gained gac intensity is listed in the table below in 1.
Embodiment 6
With the thermoset acrylonitrile resin ball of 250g, be oxidation 10 hours under 400 ℃ temperature in the atmosphere of 50 volume % in oxygen level.The above product that obtains in inert atmosphere nitrogen, is elevated to 1200 ℃ with 1 ℃/minute temperature rise rate, and under this temperature constant temperature 2 hours, carry out charing and handle.Subsequently, under 1000 ℃, carry out activation treatment under the activation phenomenon of water vapour, soak time is 0.5 hour, promptly obtains the superstrength porous microsphere active carbon.Gained gac intensity is listed in the table below in 1.
Embodiment 7
With the heat-reactive phenolic resin ball of 300g, under 300 ℃, utilized vitriol oil oxidation 8 hours.The above product that obtains in inert atmosphere nitrogen, is elevated to 1000 ℃ with 3 ℃/minute temperature rise rates, and under this temperature, stopped 2 hours, carry out charing and handle.Subsequently, under 900 ℃, carry out activation treatment under the activation phenomenon of water vapour, soak time is 1 hour, promptly obtains the superstrength porous microsphere active carbon.Gained gac intensity is listed in the table below in 1.
Embodiment 8
With thermosetting styrene and the divinyl benzene copolymer resin balls of 300g, be oxidation 10 hours under 120 ℃ temperature in the atmosphere of 30 volume % in oxygen level.The above product that obtains in inert atmosphere nitrogen, is elevated to 1100 ℃ with 1 ℃/minute temperature rise rate, and under this temperature, stopped 2 hours, carry out charing and handle.Subsequently, under 900 ℃, carry out activation treatment under the activation phenomenon of water vapour, soak time is 1 hour, promptly obtains the superstrength porous microsphere active carbon.Gained gac intensity is listed in the table below in 1.
Comparative Examples 1
With 100 gram oil is that pitch and 35 gram naphthalenes join in the pressure vessel, and under agitation melting mixing evenly forms eutectic in the back, sieves after fragmentation, forms the particle of granularity 0.02-0.35mm.Particle with the corresponding granularity in screening back places reactor, adds the polyvinyl alcohol emulsion, after the dispersed with stirring balling-up, filters water or remove polyvinyl alcohol with distilled water wash.Bitumen ball is placed container, add the normal hexane of 7 times of amounts of bitumen ball weight, under 150 rev/mins stirring, naphthalene carried and extracting, form a porous bitumen ball.Porous spherical pitch speed with 3 ℃/minute in air is warming up to 260 ℃, and constant temperature is 15 hours under 260 ℃ temperature, is not melted the porous asphalt ball.To be warming up under 900 ℃ the temperature charing with 15 ℃/point temperature rise rate through the porous asphalt ball after the melt processed not subsequently and handle, and feed water vapor simultaneously and carried out activation treatment 180 minutes, obtain porous microsphere active carbon.Gained contrast is listed in the table below in 1 with gac intensity.
Comparative Examples 2
150 gram coal-tar pitches and 40 gram naphthalenes are joined in the pressure vessel, and under agitation melting mixing evenly forms eutectic in the back, sieves after fragmentation, forms the particle of granularity 0.02-0.35mm.Particle with the corresponding granularity in screening back places reactor, adds the polyvinyl alcohol emulsion, after the dispersed with stirring balling-up, filters water or remove polyvinyl alcohol with distilled water wash.Bitumen ball is placed container, add the normal hexane of 7 times of amounts of bitumen ball weight, under 200 rev/mins stirring, naphthalene carried and extracting, form a porous bitumen ball.Porous spherical pitch speed with 3 ℃/minute in air is warming up to 300 ℃, and constant temperature is 10 hours under 300 ℃ temperature, is not melted the porous asphalt ball.To be warming up under 1000 ℃ the temperature charing with 15 ℃/point temperature rise rate through the porous asphalt ball after the melt processed not subsequently and handle, and feed water vapor simultaneously and carried out activation treatment 120 minutes, obtain porous microsphere active carbon.Gained contrast is listed in the table below in 1 with gac intensity.
The individual seed strength of the porous microsphere active carbon of table 1 embodiment 1～8 and Comparative Examples 1 and 2 preparations relatively
| Single particle intensity (MPa) | |
| Embodiment 1 | 154.21 |
| Embodiment 2 | 90.45 |
| Embodiment 3 | 70.69 |
| Embodiment 4 | 169.73 |
| Embodiment 5 | 171.81 |
| Embodiment 6 | 182.32 |
| Embodiment 7 | 177.83 |
| Embodiment 8 | 179.02 |
| Comparative Examples 1 | 46.89 |
| Comparative Examples 2 | 49.36 |
Claims (7)
- One kind improve one's methods the preparation the superstrength porous microsphere active carbon, it is characterized in that, said improve one's methods for: be in the atmosphere of 1～50 volume % in oxygen level (a) with the thermosetting resin ball, oxidation is 1～10 hour under 60 ℃～400 ℃ temperature, or with thermosetting resin under 60 ℃～300 ℃, the acid or the SO that have oxidisability at the vitriol oil, chloric acid, perchloric acid or oleum etc. 2Or SO 3Carry out pre-treatment 1～15 hour in the atmosphere of gas; (b) with the product that obtains in as helium, nitrogen or its gas mixture inert atmosphere, under 600 ℃～1200 ℃, carry out carbonizing treatment.Subsequently, under 600 ℃～1200 ℃, carry out activation treatment 10min～3 hour under the activation phenomenon of water vapour, obtaining single particle intensity is the superstrength porous microsphere active carbon of 50～200MPa.
- 2. according to the superstrength porous microsphere active carbon of the method for claim 1 preparation, it is characterized in that, said method comprises: be in the atmosphere of 5～40 volume % with commercially available thermosetting resin ball in oxygen level (a), oxidation is 1～10 hour under 80 ℃～300 ℃ temperature, or with commercially available thermosetting resin under 100 ℃～200 ℃, the acid or the SO that have oxidisability at the vitriol oil, chloric acid, perchloric acid or oleum etc. 2, SO 3Carry out pre-treatment 2～10 hours in the atmosphere of gas; (b) with above-mentioned pretreated material in such as helium, nitrogen or its mixed inert atmosphere gas, under 700 ℃～1100 ℃, carry out carbonizing treatment; (c) under 700 ℃～1100 ℃, under steam activation atmosphere, carry out activation treatment, soak time is 10 minutes～3 hours, obtains the porous microsphere active carbon that single particle intensity is 60-200Mpa.
- 3. according to the superstrength porous microsphere active carbon of the method for claim 2 preparation, it is characterized in that, said method comprises: be in the atmosphere of 10～35 volume % with commercially available thermosetting resin ball in oxygen level (a), oxidation is 5～8 hours under 150 ℃～200 ℃ temperature, or with commercially available thermosetting resin under 150 ℃～200 ℃, the acid or the SO that have oxidisability at the vitriol oil, chloric acid, perchloric acid or oleum etc. 2, SO 3Carry out pre-treatment 2～10 hours in the atmosphere of gas; (b) with above-mentioned pretreated material in such as helium, nitrogen or its mixed inert atmosphere gas, under 900 ℃～1000 ℃, carry out carbonizing treatment; (c) under 800 ℃～1000 ℃, under steam activation atmosphere, carried out activation treatment 20 minutes～2 hours, obtain the porous microsphere active carbon that single particle intensity is 100～190Mpa.
- 4. according to the superstrength porous microsphere active carbon of claim 1, the preparation of 2 or 3 method, it is characterized in that the particle diameter of the described porous microsphere active carbon that obtains is 10 μ m～2mm, the BET specific surface area is 500～4000m 2/ g.
- 5. according to the superstrength porous microsphere active carbon of claim 1, the preparation of 2 or 3 method, it is characterized in that the particle diameter of the described porous microsphere active carbon that obtains is 10 μ m～2mm, BET method specific surface area is 800-4000m 2/ g.
- 6. according to the superstrength porous microsphere active carbon of claim 1, the preparation of 2 or 3 method, it is characterized in that the particle diameter of the described porous microsphere active carbon that obtains is 10 μ m～1mm, BET method specific surface area is 1000-4000m 2/ g.
- 7. according to the superstrength porous microsphere active carbon of the method for above-mentioned arbitrary claim preparation, it is characterized in that said method comprises: said commercially available thermosetting resin ball: be the phenolic resin balls of from phenolic varnish type phenol resins, fusible type phenol resins, phenolic varnish type alkyl phenol resin or fusible type alkyl phenol resin, selecting; Or the resin balls of from phenylethylene resin series ball, acrylic resin balls, acrylic resin ball, metha crylic resin balls, polyvinylidene chloride resin ball, furane resin ball, urea resin ball, melamine resin ball or Resins, epoxy ball, selecting.
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