CN101284223A - Magnetic porous carbon adsorbent and preparation method thereof - Google Patents
Magnetic porous carbon adsorbent and preparation method thereof Download PDFInfo
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- CN101284223A CN101284223A CNA2007100109574A CN200710010957A CN101284223A CN 101284223 A CN101284223 A CN 101284223A CN A2007100109574 A CNA2007100109574 A CN A2007100109574A CN 200710010957 A CN200710010957 A CN 200710010957A CN 101284223 A CN101284223 A CN 101284223A
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- carbon adsorbent
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- adsorbent
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 33
- 239000000084 colloidal system Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000006249 magnetic particle Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract 2
- 239000011148 porous material Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 16
- 239000003610 charcoal Substances 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001338 self-assembly Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000001939 inductive effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- -1 hydroxide compound Chemical class 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000002775 capsule Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical group CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000010977 jade Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 2
- 239000004094 surface-active agent Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 24
- 238000005516 engineering process Methods 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
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- 238000001556 precipitation Methods 0.000 abstract 1
- 239000002156 adsorbate Substances 0.000 description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
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- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 229920005546 furfural resin Polymers 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 241000233866 Fungi Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
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- 238000003763 carbonization Methods 0.000 description 2
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- 230000013011 mating Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
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- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a preparation technology of carbon adsorbent, in particular to a magnetic multiporous carbon adsorbent and a preparation method. Aiming at realizing the recycling and reusing of powdery adsorbent and the high-efficient adsorption of giant-molecule organic pollutants such as dye, etc., magnetic metal hydroxide colloid is obtained from alkaline solution and is mixed with resin solution; during the process, the hydroxide colloid is a template, water is in-situ precipitation agent of resin, and a composite system of resin/hydroxide colloid is directly obtained in a liquid phase. After solvent is removed, the magnetic multiporous carbon adsorbent with mesoporous/macroporous size can be prepared, the magnetic load weight can be controlled, and the proportion can be controlled, wherein, the carbon components of the adsorbent account for 60 to 95wt percent, and the magnetic-particle components account for 5 to 40wt percent. The magnetic multiporous carbon adsorbent and the preparation method can provide a novel high-efficient method to the in-situ load of various catalyst particles, thereby having important application value in the water treatment, the photocatalysis technology, fuel cells and relative catalysis yields.
Description
Technical field
The present invention relates to the technology of preparing of carbon adsorbent, be specially a kind of magnetic porous carbon adsorbent and preparation method thereof.
Background technology
Along with the day by day dependence of human lives to chemical products, the environmental pollution that " three wastes " that Chemical Manufacture is discharged (waste water, waste residue, waste gas) cause aggravates gradually.Contaminated wastewater, such as factories such as printing and dyeing mill, paper mill dischargings contain organic matter sewage and city domestic sewage, the biosphere circulatory systems such as river, lake have been produced destruction quite serious even that be difficult to recover.These organic pollutions have weakened the light transmittance of water body on the one hand, make that the contaminative organic matter is difficult to self decompose under light action in the water body; Can make body eutrophication on the other hand, quicken the uncontrolled growth of algae, the harm aquatic animal.These factors make contaminated water body lose self detergent power substantially, and then threaten biosphere and environment for human survival.Therefore, the advanced water technology of development purifies the waste water of contaminated water body and factory's drainage, just seems particularly urgent.
The specific area height of active carbon has excellent adsorption capacity, thereby has been widely used in water technology.But, produce the difficult recovery problem of powder when being used for water treatment, and cause the secondary pollution of powder water body because active carbon macroscopic view form mostly is Powdered.Therefore development has high-specific surface area, the porous carbon material that easily reclaims becomes the key issue that the advanced water technology of development institute must solution.In addition, because present water pollutant mostly is larger molecular organics, though the specific area of active carbon is very high, pore structure is main with micropore (micropore size is 1~2nm, and micro content is 80-90%), is unfavorable for its absorption to larger molecular organics.Thereby need the pore structure of control porous carbon material rationally, and increase mesopore and macropore content, make it to go for the water technology of larger molecular organics pollution sources.
Summary of the invention
In order further to expand the application of porous carbon material in environmental protection and water treatment industry; the object of the present invention is to provide a kind of novel callable magnetic porous carbon adsorbent and preparation method thereof; solve active carbon very easy difficulty that produces powder when being used for water treatment and reclaim, inevitably cause the secondary pollution problems of powder water body; the preparation magnetic porous carbon adsorbent has mesopore (aperture is at 2-50nm), macropore (aperture greater than 50nm to several microns) and presents a kind of even distribution continuously, is applicable to the absorption to larger molecular organics.
Technical scheme of the present invention is:
The invention provides a kind of preparation method of novel magnetic porous carbon adsorbent, bring out the direct synthetic resin based compound system of magnetic metal hydroxide colloid original position separation method by mating surface activating agent in the alkaline aqueous solution system, and follow-up charing and/or activation processing prepare magnetic porous carbon adsorbent.Concrete process is that the inorganic salts of magnetic metal (transition group iron-cobalt-nickel metal) or organic salt or suitable combination thing (such as nickel nitrate, nickel acetate, nickel chloride, nickelous sulfate, cobalt acetate, cobalt nitrate, ferric nitrate etc.) fully are dissolved in water, its weight percent concentration is 5-30wt%, forms first solution system; Simultaneously, with precipitating reagent (ammoniacal liquor, urea, carbonic acid ammonia, sodium carbonate, sodium acid carbonate, weak base or NaOH such as potash, highly basic such as potassium hydroxide), self assembly inducing agent [1. block copolymer (as poly-oxireme-poly-epoxy third rare P123 etc.), 2. the anion/cation surfacant is (as 18 semi-annular jade pendants acid sodium, softex kw etc.), 3. nonionic surfactant (as ethoxylated dodecyl alcohol Brij30 etc.)] and water evenly mix dissolving (wherein proportion is 1: (0.1-5): (1-50)) fully according to the constant weight ratio, form second solution system; Then under 10-100 ℃ of condition of normal pressure with above-mentioned two solution systems by weight being 0.1-1 mixing, make the metal ion in the magnetic metal compound solution form its hydroxide colloid under precipitating reagent and the effect of self assembly inducing agent.With the ethanolic solution of colloid and alcohol-soluble resin (as phenolic resins, furfural resin etc.) is 1 by weight: (2-10) mix, the weight ratio of resin and ethanol is 1: (1-20); Drying is removed wherein water and ethanol, can prepare resin/hydroxide compound system.With this compound system charing and/or activation processing, can prepare magnetic porous carbon adsorbent.Wherein can control specific area, pore-size distribution and the microscopic appearance that obtains end product by the ratio of regulating magnesium-yttrium-transition metal salt, precipitating reagent, resin, self assembly inducing agent.
Among the present invention, the weight ratio of precipitating reagent, self assembly inducing agent and water is preferably 1: (1-3): (10-20).Among the present invention, the weight ratio of the ethanolic solution of colloid and alcohol-soluble resin is preferably 1: (2-7), the weight ratio of resin and ethanol is preferably 1: (5-10), the weight ratio of first solution system and second solution system is preferably 0.5-0.7.
The said removal solvent of the present invention, charing/activate are routine techniques.The detailed process that drying is removed wherein water and ethanol is as follows: the ethanolic solution mixture of colloid and alcohol-soluble resin was handled 24-48 hour under normal pressure at 60-80 ℃, removed wherein aqueous solvent and ethanol.
The detailed process that charing is handled is as follows:
With resin/hydroxide compound system at inertia or reducing atmosphere (Ar, N
2, H
2) in 500-1000 ℃ of temperature, heating rate is 5-10 ℃/min, temperature retention time is 2-12 hour processing.
The detailed process of activation processing is as follows:
According to requirement, adopt physically activated or chemical activating process to pore-size distribution; Wherein, physically activated employing CO
2, in steam or the air atmosphere, 300-800 ℃ following heat treatment 2-12 hour; Chemical activation adopts activator (KOH, ZnCl
2Or Fe (NO
3)
2) and the raw material of wood-charcoal material be 1 by weight: after (0.1-5) evenly mixing, at inert atmosphere (Ar, N
2) in 300-800 ℃ following heat treatment 2-12 hour, further control the combination of different apertures nano-pore.
The adsorbent that the present invention obtains consists of the porous charcoal matrix and has inlayed the magnetic-particle that is wrapped up by graphite linings, is a kind of magnetic capsule structure, and wherein the charcoal composition accounts for 60-95wt%, and the magnetic-particle composition accounts for 5-40wt%; The porous charcoal matrix is macropore-mesopore level loose structure, the microscopic appearance and the white fungus of its scanning electron microscopic observation similar (referring to Fig. 4).Characterize in conjunction with scanning electron microscopic observation and nitrogen adsorption, the aperture analysis result shows: mesopore (aperture is at 2-50nm), macropore (aperture greater than 50nm to several microns) aperture presents a kind of even distribution continuously; The volume fraction of whole pore volumes that mesopore is shared is at 20-30%, and the volume fraction of whole pore volumes that macropore is shared is at 50-60%; All the other pore volumes are micropore (aperture<2nm); The specific area of adsorbent is 100~500m
2/ g.This magnetic porous carbon adsorbent has the meso/macroporous structure that good magnetic can realize contactless stalling characteristic and optimization, is expected to be used widely in water technology as callable powdery porous carbon adsorbent.
The invention has the beneficial effects as follows:
1, the present invention proposes a kind of mentality of designing of novel magnetic porous carbon adsorbent.Reclaim, there is secondary powder pollution problems in water body for the powdered absorbent difficulty that water treatment faced, propose by coating/carried magnetic particle in porous carbon adsorbent, utilize the contactless isolation technics of magnetic then, the adsorbent powder is reclaimed from water body, pass through separating treatment, make the magnetic porous carbon adsorbent can recycled for multiple times, in the secondary powder pollution problem of having avoided water body, also help to economize in raw materials, reduce cost.For the mass transfer and the adsorption process of the related adsorbate of water technology, the mass transfer rate of adsorption molecule in the porous charcoal structure restricting adsorption efficiency.Therefore the diffusion admittance that needs the appropriate design adsorption molecule can be realized by the pore structure and the controlled pore structure route of synthesis of development of appropriate design porous carbon material.For present commonplace big molecule organic pollution situation, have only mesopore and macropore just to help the mass transfer of the big molecule organic pollution of this class adsorbate.And, because these macromolecular diameters are distributed in 1~3nm, have only mesopore can provide size suitable adsorption potential.The loose structure of appropriate design mesopore/macropore can effectively improve the absorption of larger molecular organics adsorbate.Although traditional chemical/physically activated method can prepare the active carbon with certain mesopore content, mesopore aperture wherein is less relatively, and content is relatively low, has limited the raising of its performance and widening of range of application.And adopt mesoporous molecular sieve is that the technology of template has long, shortcomings such as cost is high, structure poor reproducibility of cycle, is unfavorable for extensive utilization.In addition, above-mentioned two kinds of approach are difficult in the porous charcoal structure introduces macropore, thereby has limited the mass transfer of adsorption molecule.
Method of the present invention can controlledly synthesis has the magnetic porous carbon structure of different content mesopore, macropore and magnetic-particle, and the needed raw material wide material sources are cheap, and technology is simple, the structure favorable reproducibility.
2, the magnetic metal hydroxide colloid and the direct synthetic resin of the alcohol-soluble resin original position separation method/hydroxide composite that bring out by mating surface activating agent self assembly in the alkaline aqueous solution system of the present invention.The magnetic porous carbon adsorbent of the method for this composite charing and activation preparation had higher specific surface area, large scale adsorption molecule transmission channel fast, can obtain magnetic, can realize that contactless separating power reaches larger molecular organics adsorption capacity efficiently.
3, the magnetic-particle load capacity of the synthetic magnetic porous carbon adsorbent of the inventive method is controlled in the 5-40wt% scope, and mesopore (aperture is at 2-50nm), macropore (aperture greater than 50nm to several microns) aperture presents a kind of even distribution continuously; The volume fraction of whole pore volumes that mesopore is shared is at 20-30%, and the volume fraction of whole pore volumes that macropore is shared is at 50-60%; The specific area of adsorbent is 100~500m
2/ g.The novel magnetic porous carbon adsorbent that the present invention synthesizes has the recyclable characteristic of Magnetic Isolation and to the efficient adsorption capacity of big molecule organic pollution.Realized the target of original position coating/carried magnetic particle in the porous charcoal structure in view of such magnetic porous carbon adsorbent, the design preparation method of this novelty must provide new and effective new way for the original position load of various catalyst granules, and thereby has far-reaching using value and Research Significance at photocatalysis technology, fuel cell and relevant catalytic field.
4, the invention provides a kind of approach for preparing advanced novel magnetic porous carbon adsorbent.Key of the present invention is on the recycling of taking all factors into consideration powdered absorbent and the basis to the efficient adsorption capacity of big molecule organic pollution such as dye molecule, has proposed a kind of route of synthesis of novel magnetic porous carbon adsorbent.The design philosophy of this novel magnetic porous carbon adsorbent is the comprehensive utilization separable characteristic of magnetic-particle and mesopore, the macropore adsorption capacity to larger molecular organics, propose a kind of can original position coating/carried magnetic particle and control the novel route of synthesis of the pore-size distribution of loose structure.Main feature of the present invention is directly to synthesize the compound of hydroxide colloid/resin by combining hydrogen oxidation thing colloid in water solution system and original position separation method, and this compound charing/activation is prepared the magnetic porous adsorbent with above-mentioned novel characteristics.
Description of drawings
Fig. 1 is the XRD figure spectrum of magnetic porous carbon adsorbent.
Fig. 2 is the hysteresis curve of magnetic porous carbon adsorbent.
Fig. 3 is the isothermal nitrogen adsorption curve and the pore distribution curve (inserting figure) of magnetic porous carbon adsorbent.
Fig. 4 is the magnetic porous carbon adsorbent electron scanning micrograph.
The specific embodiment
With magnetic porous charcoal of the present invention is adsorbent, is big molecular dye adsorbate with methylene orange and rhodamine-B, the water treatment capacity of having tested such material.
Below in conjunction with embodiment the present invention is illustrated:
Embodiment 1
Nickel nitrate is dissolved in water, and its weight concentration is 10%, forms first solution system; With NaOH, P123, water forms second solution system according to certain weight ratio dissolving fully in 1: 3: 10; Then, under 20 ℃ of condition of normal pressure, be mixing in 1: 1 by weight with above-mentioned two solution systems, under the highly basic effect, form its hydroxide colloid; Add 20wt% alcohol-soluble resin (phenolic resins), colloid and alcohol-soluble resin weight ratio are 1: 2.5; Remove solvent, just can obtain resin/hydroxide composite, in addition charing promptly gets magnetic porous carbon adsorbent.The BET specific area of the material that obtains reaches 263m
2/ g, the magnetic-particle load capacity is 38wt%, the mesopore aperture is 4-50nm, mesopore volume content accounts for 20%, and macropore diameter is 51-2000nm, and macropore volume content accounts for 60%, continuous, the evenly distribution of mesopore and big hole dimension is inserted figure referring to Fig. 3, and all the other pore volumes are aperture<2nm micropore.
Removal of solvents in the present embodiment, charing are routine techniques.Wherein,
The detailed process of removal of solvents is as follows: with the ethanolic solution mixture of colloid and alcohol-soluble resin at 80 ℃ of slowly evaporative removal aqueous solvent and ethanol (24 hours) under normal pressure.
The detailed process of charing is as follows: with colloidal dispersion charing in argon gas earlier, carbonization temperature is at 600 ℃, and heating rate is 10 ℃/min, carbonization time be 4 hours the raw material of wood-charcoal material.Present embodiment is activation processing not.
The XRD figure of magnetic porous carbon adsorbent as shown in Figure 1 spectrum shows that this material is made up of charcoal and nickel.
The hysteresis curve of magnetic porous carbon adsorbent as shown in Figure 2 shows that this material has certain saturation magnetization and coercivity.
The isothermal nitrogen adsorption curve of magnetic porous carbon adsorbent as shown in Figure 3 and pore distribution curve (insert figure) show that the mesopore of this material and macropore ratio are up to 80%.
Magnetic porous carbon adsorbent electron scanning micrograph as shown in Figure 4 (scale is 1 micron among the figure), from morphology observation, the magnetic porous carbon adsorbent structure is as follows: have the big pore size distribution of likeness in form white fungus, big hole dimension micron does not wait from hundreds of nanometer to two or three.
With it is adsorbent, and the methylene orange is an adsorbate, and the test saturated extent of adsorption can reach 43mg/g, and reaching the adsorption equilibrium time is 15min.
Difference from Example 1 is:
Nickel nitrate is dissolved in water, and its weight concentration is 5%, forms first solution system; NaOH, P123, water forms second solution system according to certain weight ratio dissolving fully in 1: 3: 10; Then, under 20 ℃ of condition of normal pressure, be mixing in 0.5: 1 by weight with above-mentioned two solution systems, under the highly basic effect, form its hydroxide colloid; Add 20wt% alcohol-soluble resin (phenolic resins), colloid and alcohol-soluble resin weight ratio are 1: 2.5; Remove solvent, just can obtain resin/hydroxide composite, in addition charing promptly gets magnetic porous carbon adsorbent.The BET specific area of the material that obtains reaches 263m
2/ g, the magnetic-particle load capacity is 38wt%, and the mesopore aperture is 4-50nm, and mesopore volume content accounts for 20%, and macropore diameter is 51-2000nm, and macropore volume content accounts for 60%, and continuous, the evenly distribution of mesopore and big hole dimension is inserted figure referring to Fig. 3.All the other pore volumes are aperture<2nm micropore.
With it is adsorbent, and rhodamine-B is an adsorbate, and the test saturated extent of adsorption can reach 36mg/g, and reaching the adsorption equilibrium time is 20min.
Embodiment 3
Difference from Example 1 is:
Cobalt nitrate is dissolved in water, and its weight concentration is 20%, forms first solution system; NaOH, P123, water mixes dissolving fully according to certain weight ratio at 1: 2: 10, forms second solution system; Under 20 ℃ of condition of normal pressure, be mixing in 0.8: 1 by weight then, form its hydroxide colloid in the highly basic effect with above-mentioned two solution systems; Add 20wt% alcohol-soluble resin (furfural resin), colloid and alcohol-soluble resin weight ratio are 1: 5; Remove solvent, just can obtain resin/hydroxide composite, in addition charing promptly gets magnetic porous carbon adsorbent.The BET specific area of the material that obtains reaches 157m
2/ g, the magnetic-particle load capacity is 40wt%, and the mesopore aperture is 4-50nm, and mesopore volume content accounts for 30%, and macropore diameter is 51-1500nm, macropore volume content accounts for 50%, continuous, the evenly distribution of mesopore and big hole dimension, all the other pore volumes are aperture<2nm micropore.
With it is adsorbent, and the methylene orange is an adsorbate, and the test saturated extent of adsorption can reach 45mg/g, and reaching the adsorption equilibrium time is 32min.
Embodiment 4
Difference from Example 1 is:
Ferric nitrate is dissolved in water, and its weight concentration is 30%, forms first solution system; NaOH, P123, water mixes dissolving fully according to certain weight ratio at 2: 3: 10, forms second solution system; Under 20 ℃ of condition of normal pressure, be mixing in 1: 1 by weight then, form its hydroxide colloid in the highly basic effect with above-mentioned two solution systems; Add 20wt% alcohol-soluble resin (furfural resin), colloid and alcohol-soluble resin weight ratio are 1: 3; Remove solvent, just can obtain resin/hydroxide composite, in addition charing, activation promptly get magnetic porous carbon adsorbent; Present embodiment adopts chemical activation according to the requirement of pore-size distribution, and the weight ratio of activator KOH and raw material of wood-charcoal material is 1: 1,500 ℃ of activation 4 hours down in argon gas atmosphere (heating rate be 10 ℃/min), can further control the combination of different apertures nano-pore.The BET specific area of the material that obtains reaches 205m
2/ g, the magnetic-particle load capacity is 37wt%, and the mesopore aperture is 3-50nm, and mesopore volume content accounts for 25%, and macropore diameter is 51-2200nm, macropore volume content accounts for 55%, continuous, the evenly distribution of mesopore and big hole dimension.All the other pore volumes are aperture<2nm micropore.
With it is adsorbent, and the methylene orange is an adsorbate, and the test saturated extent of adsorption can reach 38mg/g, and reaching the adsorption equilibrium time is 45min.
Claims (8)
1, a kind of magnetic porous carbon adsorbent, it is characterized in that: this adsorbent is the magnetic-particle of having inlayed in the porous charcoal particle by the graphite linings parcel, be a kind of magnetic capsule structure, the charcoal ingredients constitute 60-95wt% of adsorbent wherein, magnetic-particle ingredients constitute 5-40wt%; The porous charcoal matrix has the level pore structure of macropore-mesopore, and the aperture presents a kind of continuous even distribution in mesopore, the aperture of 2-50nm at the macropore greater than 50nm to 10 micron; The volume fraction of whole pore volumes that mesopore is shared is at 20-30%, and the shared whole pore volume volume fractions of macropore are at 50-60%, and all the other pore volumes are the micropore of aperture less than 2nm; The specific area of adsorbent is 100~500m
2/ g.
2, according to the preparation method of the described magnetic porous carbon adsorbent of claim 1, it is characterized in that: in the alkaline aqueous solution system, adopt surfactant to bring out the method that magnetic metal hydroxide colloid original position is separated out, directly obtain the resin-based compound system, and obtain magnetic porous carbon adsorbent through charing and/or activation processing; Concrete process is:
(1) inorganic salts of magnetic metal or organic salt or compound fully are dissolved in water and form first solution system, its weight percent concentration is 5-30wt%; With precipitating reagent, self assembly inducing agent and water, according to part by weight 1: (0.1-5): (1-50) evenly mix dissolving fully, form second solution system, the self assembly inducing agent is block copolymer, zwitterion surfacant or nonionic surfactant; Then under 10-100 ℃ of condition of normal pressure with above-mentioned first solution system and second solution system by weight for the 0.1-1 mixing, under precipitating reagent and the effect of self assembly inducing agent, make the metal ion in the magnetic metal compound solution form its hydroxide colloid;
(2) with the ethanolic solution of colloid and alcohol-soluble resin according to by weight 1: (2-10) mix, the weight ratio of resin and ethanol is 1 in the ethanolic solution of resin: (1-20); Drying is removed wherein water and ethanol, can prepare resin/hydroxide compound system; With this compound system charing and/or activation, prepare magnetic porous carbon adsorbent.
3, according to the preparation method of the described magnetic porous carbon adsorbent of claim 2, it is characterized in that, in the described step (2), the detailed process that drying is removed wherein water and ethanol is as follows: the ethanolic solution mixture of colloid and alcohol-soluble resin was handled 24-48 hour under normal pressure at 60-80 ℃, obtained resin/hydroxide compound system.
According to the preparation method of the described magnetic porous carbon adsorbent of claim 2, it is characterized in that 4, in the described step (2), the detailed process of charing is as follows: with resin/hydroxide compound system at inertia or reducing atmosphere Ar, N
2Or H
2In, interval 500-1000 ℃ of holding temperature, heating rate is 5-20 ℃/min, temperature retention time is 2-12 hour processing.
According to the preparation method of the described magnetic porous carbon adsorbent of claim 2, it is characterized in that 5, in the described step (2), the detailed process of activation is as follows:, adopt physically activated or chemical activating process according to needs to pore-size distribution; Wherein, physically activated employing is at CO
2, in steam or the air atmosphere, 300-800 ℃ following heat treatment 2-12 hour; Chemical activation adopts activator KOH, ZnCl
2Or Fe (NO
3)
2With the raw material of wood-charcoal material is 1 by weight: after (0.1-5) evenly mixing, in inert atmosphere 300-800 ℃ following heat treatment 2-12 hour.
6, according to the preparation method of the described magnetic porous carbon adsorbent of claim 2, it is characterized in that: the inorganic salts of magnetic metal or the compound of organic salt are nickel nitrate, nickel acetate, nickel chloride, nickelous sulfate, cobalt acetate, cobalt nitrate or ferric nitrate.
According to the preparation method of the described magnetic porous carbon adsorbent of claim 2, it is characterized in that 7, precipitating reagent comprises: ammoniacal liquor, urea, carbonic acid ammonia, sodium carbonate, sodium acid carbonate, potash, NaOH or potassium hydroxide.
According to the preparation method of the described magnetic porous carbon adsorbent of claim 2, it is characterized in that 8, the self assembly inducing agent is block copolymer, zwitterion surfacant or nonionic surfactant; Block copolymer is poly-oxireme-poly-epoxy third rare P123; The anion/cation surfacant is 18 semi-annular jade pendants acid sodium or softex kw; Nonionic surfactant is ethoxylated dodecyl alcohol Brij30.
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