EP1091801A1 - Aus nanokristallen hergestellte poröse pellet-adsobentien - Google Patents

Aus nanokristallen hergestellte poröse pellet-adsobentien

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Publication number
EP1091801A1
EP1091801A1 EP99927082A EP99927082A EP1091801A1 EP 1091801 A1 EP1091801 A1 EP 1091801A1 EP 99927082 A EP99927082 A EP 99927082A EP 99927082 A EP99927082 A EP 99927082A EP 1091801 A1 EP1091801 A1 EP 1091801A1
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EP
European Patent Office
Prior art keywords
powder
composite
mgo
psi
surface area
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99927082A
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English (en)
French (fr)
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EP1091801A4 (de
Inventor
Kenneth J. Klabunde
Olga Koper
Abbas Khaleel
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Kansas State University
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Kansas State University
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Publication date
Priority claimed from US09/093,249 external-priority patent/US6093236A/en
Application filed by Kansas State University filed Critical Kansas State University
Publication of EP1091801A1 publication Critical patent/EP1091801A1/de
Publication of EP1091801A4 publication Critical patent/EP1091801A4/de
Withdrawn legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041Oxides or hydroxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078Pore diameter
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28095Shape or type of pores, voids, channels, ducts
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3021Milling, crushing or grinding
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3035Compressing
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
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    • B01D2253/112Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
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    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
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    • B01D2253/308Pore size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
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    • B01D2257/2064Chlorine
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    • B01D2257/404Nitrogen oxides other than dinitrogen oxide
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    • B01D2257/702Hydrocarbons
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01D2258/0225Other waste gases from chemical or biological warfare

Definitions

  • the present invention is broadly concerned with pelletized finely divided adsorbents selected from the group consisting of metal oxides, metal hydroxides, and mixtures thereof, and methods of forming such pellets.
  • the pellets are preferably formed by pressing the finely divided metal adsorbents at pressures of from about 50 psi to about 6000 psi to yield self-sustaining bodies which retain at least about 25% of the surface area/unit mass and total pore volume of the starting metal adsorbents prior to pressing thereof.
  • target compound(s) are contacted with adsorbent pellets of the invention to destructively adsorb or chemisorb the target compound(s).
  • Activated carbon has been the most commonly used in dealing with purification of air.
  • the highest quality activated carbon is made from coconut shells and has a surface area/unit mass of about 600-900 m 2 /g.
  • activated carbon does not strongly adsorb air pollutants and the adsorbed material can be released over time with continued air flow.
  • activated carbon is difficult to clean up.
  • Electrostatic filters work well at removing particulates from the indoor air. However, electrostatic filters are inadequate at removing many chemical vapors from the air, and there are numerous chemical vapor air pollutants which are of concern. The most prevalent of these include formaldehyde, acetaldehyde, methanol, methylene chloride, carbon tetrachloride, carbon monoxide, dimethyl amine, toluene, benzene, sulfur dioxide, acetonitrile, nitrosoamine, and nitrogen dioxide.
  • Nanocrystals make up a high surface area form of matter that can serve as another adsorbent which can be used for removing pollutants such as chlorocarbons, acid gases, military warfare agents, and insecticides from the air.
  • pollutants such as chlorocarbons, acid gases, military warfare agents, and insecticides from the air.
  • the unique chemical reactivity of nanocrystals allows the destructive adsorption and chemisorption of toxic substances and are a substantial advance in air purification.
  • nanocrystals are a very fine dust which take up large volumes of space and are conducive to electrostaticity, thus making them difficult to handle and at times inconvenient.
  • adsorbent compound capable of strongly adsorbing air pollutants which does not release those pollutants over time. Furthermore, this adsorbent compound must be easy to handle and be of decreased volume compared to nanocrystal adsorbents.
  • the present invention overcomes these problems and provides adsorbent pellet bodies and methods for adsorbing a wide variety of target compounds using such pellet bodies.
  • the invention contemplates the use of adsorbent pellets which are formed by pressing finely divided adsorbents. Adsorbent reactions using the inventions can be carried out over a wide range of temperatures, but preferably the temperature is such that the target compounds are in gaseous form.
  • the adsorbent pellets of the invention are formed by pressing or agglomerating a quantity of finely divided adsorbent powder selected from the group consisting of metal hydroxides, metal oxides, and mixtures thereof. More preferably, the powder is an oxide or hydroxide of Mg, Ca, Ti, Zr, Fe, V, Mn, Ni, Cu, Al, or Zn. Metal oxides are the most preferred adsorbent powder with MgO and CaO being particularly preferred. While conventionally prepared powders can be used to form the pellets, the preferred powders are prepared by aerogel techniques from Utamapanya et a ⁇ ., Chem. M ⁇ ter., 3:175-181 (1991).
  • the starting powders should advantageously have an average crystallite size of up to about 20 nm, and more preferably from about 3 to 9 nm.
  • the pellets of this invention are formed by pressing the adsorbent powder at a pressure of from about 50 psi to about 6000 psi, more preferably from about 500 psi to about 5000 psi, and most preferably at about 2000 psi. While pressures are typically applied to the powder by way of an automatic or hydraulic press, one skilled in the art will appreciate that the pellets can be formed by any pressure-applying or other agglomerating means (e.g., centrifugal or vibratory agglomerators).
  • a binder or filler can be mixed with the adsorbent powder and the pellets can be formed by pressing the mixture by hand.
  • Agglomerating or agglomerated as used hereinafter includes pressing together of the adsorbent powder as well as pressed-together adsorbent powder. Agglomerating also includes the spraying, adhering, centrifugation, vibration or pressing of the adsorbent powder (either alone or in a mixture) to form a body, which may optionally be formed around a core material other than the adsorbent powder.
  • the adsorbent powders of the invention can be embedded in or supported on a porous substrate such as a filtration media.
  • the corresponding metal hydroxide should be thermally converted (i.e., "activated" at 500 °C, overnight in a vacuum) to the metal oxide form. Activation can be carried out either on the metal hydroxide powder or on the finished metal hydroxide pellet. However, it is preferred that the metal hydroxide first be pressed into a pellet followed by thermal conversion to a metal oxide pellet.
  • the pellets of the invention should retain at least about 25% of the multi-point surface area/unit mass of the metal hydroxide or metal oxide (whichever was used to form the pellet) particles prior to pressing together thereof. More preferably, the multi- point surface area/unit mass of the pellets will be at least about 50%, and most preferably at least about 90%, of the multi-point surface area/unit mass of the starting metal oxide or metal hydroxide particles prior to pressing. In another embodiment, the pellets retain at least about 25% of the total pore volume of the metal hydroxide or metal oxide particles prior to pressing thereof, more preferably, at least about 50%, and most preferably at least about 90% thereof. In the most preferred forms, the pellets of this invention will retain the above percentages of both the multi-point surface area/unit mass and the total pore volume.
  • the preferred pelletized adsorbents should have an average pore radius of at least about 45 A, more preferably from about 50 A to about 100 A, and most preferably from about 60 A to about 75 A.
  • the pellets of this invention normally have a density of from about .2 to about 2.0 g/cm 3 , more preferably from about .3 to about 1.0 g/cm 3 , and most preferably from about .4 to about .7 g/cm 3 .
  • the minimum surface-to-surface dimension of the pellets (e.g., diameter in the case of spherical or elongated pellet bodies) of this invention is at least about 1 mm, more preferably from about 10-20 mm.
  • the use of the pelletized adsorbents in accordance with the invention is carried out by contacting the adsorbent powders with a target compound in fluid (i.e., liquid or gaseous) form.
  • a target compound in fluid (i.e., liquid or gaseous) form.
  • Preferable contacting systems include any type of flow reactor which allows a fluid stream containing the target compound to be circulated through a mass of pellets.
  • Another suitable contacting system includes forming a membrane which contains the pelletized adsorbents and using the membrane to filter the target compound from a gas or liquid. The contacting step can take place over a wide range of temperatures and pressures; however, it is preferable that the temperature be such that the conveying stream and target compound are in a gaseous form.
  • target compounds can be adsorbed using the techniques of the invention.
  • These target compounds broadly include any compounds which can be adsorbed, either destructively adsorbed or chemisorbed, by the starting metal hydroxide or metal oxide powder. More particularly, these target compounds may be selected from the group consisting of acids, alcohols, aldehydes, compounds containing an atom of P, S, N, Se or Te, hydrocarbon compounds (e.g., both halogenated and non- halogenated hydrocarbons), and toxic metal compounds.
  • Figure 1 is a graph depicting the adsorption of acetaldehyde on pelletized AP-
  • Fig. 2 is a graph illustrating the adsorption of acetaldehyde onto powder AP- MgO in comparison to the adsorption of acetaldehyde onto activated carbon;
  • Fig. 3 is a graph illustrating the adsorption of acetaldehyde onto powder AP- MgO, powder CP-MgO, and powder CM-MgO;
  • Fig.4 is a graph depicting the adsorption of acetaldehyde onto powder AP-MgO after exposure to air for varying lengths of time versus the adsorption of acetaldehyde onto activated carbon exposed to air for varying lengths of time;
  • Fig.5 is a graph comparing the adsorption of propionaldehyde onto powder AP- MgO under atmospheric pressure of air with the adsorption of propionaldehyde onto commercial samples of activated carbon under atmospheric pressure of air;
  • Fig. 6 is a graph comparing the adsorption of dimethylamine onto powder AP- MgO under atmospheric pressure of air with the adsorption of dimethylamine onto activated carbon under atmospheric pressure of air
  • Fig. 7 is a graph illustrating the adsorption of ammonia onto powder AP-MgO both with and without exposure to air and comparing this adso ⁇ tion to adsorption of ammonia onto activated carbon both with and without exposure to air;
  • Fig. 8 is a graph which depicts the adso ⁇ tion of methanol onto powder AP- MgO under one atmosphere pressure of air compared to the adso ⁇ tion of methanol onto activated at one atmosphere pressure of air.
  • Example 1 adsorbent AP-Mg(OH) 2 pellets were prepared and their surface characteristics were determined. These characteristics were compared to the characteristics of AP-Mg(OH) 2 in its powder form.
  • Highly divided nanocrystalline Mg(OH) 2 samples were prepared by the autoclave treatment described by Utamapanya et al., Chem. Mater. , 3:175-181 (1991), inco ⁇ orated by reference herein. In this procedure, 10% by weight magnesium methoxide in methanol solution was prepared and 83% by weight toluene solvent was added. The solution was then hydrolyzed by addition of 0.75%) by weight water dropwise while the solution was stirred and covered with aluminum foil to avoid evaporation. To insure completion of the reaction, the mixture was stirred overnight.
  • the AP-Mg(OH) 2 powder prepared as set forth above was ground, using a mortar and pestle, to remove any clumped powder. A portion of the powder was then placed in a small hydraulic press to make spherical 12 mm diameter pellets. Pressures ranging from 1000 psi to 10,000 psi were applied to form the pellets. The resulting pellets were crushed through sieves to form smaller pellets in order to facilitate the measuring of the surface characteristics (the sieve size was 0.25-1.168 mm).
  • a second portion of the AP-Mg(OH) 2 powder was pelletized using a Stokes automatic press.
  • the actual pressure applied is not known because the Stokes press did not have a gauge.
  • the actual pressure applied to prepare the pellets is reproducible by controlling the movement of the upper punch on the pelletizer which has a scale.
  • Low compression is just enough pressure to allow the sample to be handled without crumbling.
  • High compression is the maximum compression that can be used without jamming the machine or causing pellets to crack as they are ejected.
  • Medium is the setting approximately halfway between low and high.
  • the surface area/unit mass for the multiple BET decreased from 346 m 2 /g for the powder to 4.16 m 2 /g for the 10,000 psi pellets. The same was seen for the single point BET surface area/unit mass, which went from 635 m 2 /g for the powder to 8.29 m 2 /g for the 10,000 psi pellets.
  • the total pore volume also decreased from 0.956 cc/g for the powder to 0.01217 cc/g for the 10,000 psi pellets.
  • the average pore radius was affected very little with change in the pressure. There was however a significant change in the isotherm curves, which indicates a change in pore shape.
  • the powder sample (before pelletization) looked almost identical to the sample subjected to a pressure of 1,000 psi. The results are illustrated in Table 1.
  • Table 1 Surface area/unit mass and pore size distribution of magnesium hydroxide in powder and pellet form, prepared using the hydraulic press.
  • Pore shape type abbreviation are as follows A - Cylindrical pores, open at both ends, D - Tapered or wedged- shaped pores with narrow necks opened at one or both ends, and E - Bottleneck pores
  • Table 1 demonstrates that the surface characteristics change a great deal depending on formation pressure. It is noted that in going from the powder to the pellet compressed at 1 ,000 psi, the surface area/unit mass and pore size changed only a little; therefore, these pellets can be used in any type of flow reactor. In conclusion, it was found that the 1,000 psi pellets of AP-Mg(OH) 2 worked ideally by eliminating the problem caused by electrostatic forces, without losing a significant amount of surface area/unit mass or pore volume. b. Pellets Formed by Stokes Automatic Press
  • pelletization did not significantly decrease the surface areas/unit mass and porosities of the AP-Mg(OH) 2 . In some instances the surface area/unit mass was even higher than that of the powder.
  • the pellets made with low compression were very brittle and, after activation (heating at 500 ° C under vacuum), they turned into powder.
  • the medium compression pellets were much better, and only a small amount of powder was present after activation.
  • the pellets formed by high compression were sturdy and did not break or form powder upon activation. Therefore, the medium and high compression pellets are ideal. Because the Stokes press did not include a pressure gauge, the exact value of the pressure used in the high compression test is not known. However, in comparing the pellet characteristics of Table 2 with those of Table 1, the high compression is likely around 2000 psi.
  • adsorbent AP-MgO pellets (one sample activated in its pellet form and one sample activated in its powder form) were prepared from AP-Mg(OH) 2 powder and their physical characteristics were determined. These characteristics were compared to the characteristics of AP-MgO in its powder form. The pu ⁇ ose of this test was to determine whether the AP-MgO pellets would maintain substantially the same surface characteristics when activated in its pellet form as when activated in the powder form. It is preferable to pelletize the hydroxide first, and then activate the pellets, which converts the pellets to the oxide. Materials and Methods
  • Highly divided nanocrystalline Mg(OH) 2 samples were prepared by the autoclave treatment described by Utamapanya et al., Chem. Mater., 3:175-181 (1991), inco ⁇ orated by reference herein. In this procedure, 10% by weight magnesium methoxide in methanol solution was prepared and 83%) by weight toluene solvent was added. The solution was then hydrolyzed by addition of 0.75% by weight water dropwise while the solution was stirred and covered with aluminum foil to avoid evaporation. To insure completion of the reaction, the mixture was stirred overnight.
  • the Mg(OH) 2 powder was then divided into two parts - one part for pelletization followed by activation, and one part for activation followed by pelletization.
  • Mg(OH) 2 particles of the latter sample was then thermally converted to MgO. This was accomplished by heating the Mg(OH) 2 under dynamic vacuum (10 '2 Torr) conditions at an ascending temperature rate to a maximum temperature of 500° C which was held for 6 hours. Further details about the MgO preparation can be found in PCT Publication WO 95/27679, also inco ⁇ orated by reference herein.
  • Magnesium hydroxide powder and magnesium oxide powder were each separately ground, using a mortar and a pestle, to remove any clumped powder. A portion of each powder was separately pelletized using the Stokes automatic press resulting in AP-Mg(OH) 2 pellets and AP-MgO pellets. The actual pressure applied is unknown because the Stokes press did not have a gauge. However, the actual pressure applied to prepare the pellets is reproducible by controlling the movement of the upper punch on the pelletizer which has a scale. Low compression is just enough pressure to allow the sample to be handled without crumbling. High compression is the maximum compression that can be used without jamming the machine or causing pellets to crack as they are ejected. Medium is the setting approximately halfway between low and high.
  • the AP-Mg(OH) 2 pellets were thermally converted to AP-MgO pellets in the same manner in which the AP-Mg(OH) 2 powder was activated as described above.
  • Example 3 In this test, surface and pore characteristics of conventionally prepared MgO and
  • MgO pellets were compared to that of MgO powder.
  • AP-Mg(OH) 2 powder was prepared and thermally activated to AP-MgO powder as described above.
  • MgO pellets (pressed at 4000 psi and activated after pelletization) were also prepared as described above.
  • the adso ⁇ tion conditions and procedure followed were the same for the pellet as for the powder.
  • Each sample was placed in the U-tube of a conventional Recirculating Reactor.
  • the reactor contained a circulation pump which continually passed the gaseous acetaldehyde over and through the adsorbents. Samples were taken at set time intervals and the pollutant content was analyzed.
  • the contacting step was carried out for about 24 hours. For some experiments, air was added to the acetaldehyde vapor.
  • Fig. 1 graphically illustrates the adso ⁇ tion of acetaldehyde on powder and pelletized samples of AP-MgO. Over a period of twenty hours, the efficiency of adso ⁇ tion on the two samples was very similar. The adso ⁇ tion on the pelletized samples evolved considerable amounts of heat just as in the adso ⁇ tion on the powder samples. Furthermore, the adso ⁇ tion on both the pellets and the powder caused the sample color to change to dark orange. This further indicates that the pelletized AP- MgO has retained the surface characteristics and thus the adso ⁇ tive abilities of powder AP-MgO.
  • Example 4 This test, in combination with the results from Example 4, illustrates the superior adso ⁇ tive abilities of AP-MgO pellets in comparison to activated carbon, a prior art adsorbent.
  • pelletized AP-MgO has adso ⁇ tive abilities very similar to powder AP-MgO.
  • This Example illustrates that powder AP- MgO is substantially superior to activated carbon in its adso ⁇ tive abilities. Therefore, pelletized AP-MgO is also substantially superior to activated carbon in its adso ⁇ tive abilities.
  • the adso ⁇ tion conditions and procedures followed were identical to those described in Example 4.
  • the results are shown graphically in Fig. 2.
  • the powder AP-MgO adsorbed substantially more acetaldehyde than the activated carbon, particularly at the twenty hour point.
  • the pelletized AP-MgO has surface characteristics and adso ⁇ tive abilities comparable to the powder AP-MgO. Therefore, the pelletized AP-MgO has the adso ⁇ tive qualities of the powder AP-MgO as well as the reduced volume and greater ease of handling not found in the powder AP-MgO. It follows that the results of the following examples will be applicable to the AP-MgO pellets as well as to the AP-MgO powder.
  • Example 6 The ability of powder AP-MgO, CP-MgO, and CM-MgO to adsorb acetaldehyde was analyzed in the absence of air. Each sample was placed in the U-tube of a conventional Recirculating Reactor. The reactor contained a circulation pump which continually passed the gaseous acetaldehyde over and through the adsorbents. Samples were taken at set time intervals and the pollutant content was analyzed. The contacting step was carried out for about 20 hours. The results of this experiment are depicted in Figure 3. One mole of AP-MgO adsorbed one mole of acetaldehyde at room temperature over a short period of time.
  • the adso ⁇ tion was exothermic with a considerable amount of heat being evolved.
  • the color of the solid sample changed dramatically from a whitish-gray before adso ⁇ tion to a dark orange after adso ⁇ tion. While adso ⁇ tion was rapid and vigorous onto the AP-MgO and CP-MgO samples, it was barely observable on the CM-MgO sample where no heat or color changes were observed.
  • Example 9 An experiment was conducted to determine the ability of powder AP-MgO to adsorb dimethylamine compared with the ability of activated carbon to adsorb dimethylamine.
  • the molar ratio of adsorbent to dimethylamine was 10:1.
  • the adso ⁇ tion conditions and procedures followed were as described in Example 8 except that gaseous dimethylamine was recirculated over and through the adsorbents under atmospheric pressure of air for about 20 hours.
  • the AP-MgO adsorbed more dimethylamine than the activated carbon samples. Pelletized AP-MgO will achieve substantially the same results as the powder AP-MgO.
  • Example 10 An experiment was conducted to determine the ability of powder AP-MgO to adsorb ammonia compared with the ability of activated carbon to adsorb ammonia.
  • the molar ratio of adsorbent to ammonia was 10:1.
  • the adso ⁇ tion conditions and procedures followed were as described in Example 8 except that gaseous ammonia was recirculated over and through the adsorbents for about 20 hours both under air and in the absence of air.
  • the AP-MgO adsorbed more ammonia than the activated carbon samples. While the ammonia was adsorbed in lesser amounts than the aldehydes, it was adsorbed at a rapid rate. Pelletized AP-MgO will achieve substantially the same results as the powder AP-MgO.
  • Example 11 An experiment was conducted to determine the ability of powder AP-MgO to adsorb ammonia compared with the ability of activated carbon to adsorb ammonia.
  • the metal hydroxide powder is granulated in a Colton Model 561 Rotary Wet Granulator to generate spherical particles of about 10 mm in diameter. These particles are granulated through an addition of small amounts of water. The minimum amount of water is used to start the growth of granules.
  • Granules of the hydroxide after some drying in air or inert atmosphere are activated to oxides, which regenerates the high surface area. This is accomplished by heating the Mg(OH) 2 under dynamic vacuum (10 "2 Torr) conditions at an ascending temperature rate to a maximum temperature of 500° C which is held for 6 hrs.
  • Example 13 Production of Metal Oxide Powder-Enhanced HEP A Filter Using Spray Granulation A mark 20 HEPA from Natural Solutions is impregnated using high surface area metal oxides.
  • Metal oxides can be applied to the filter substrate by spraying metal oxide or hydroxide mixed with water, or other solvent. In this technique, water or solvent droplets adhere to the filter substrate, forming a porous layer of powder bound to the filter. In case water is used and there is significant conversion from oxide to hydroxide, the filter has to be activated. Processing under vacuum to reactivate the oxide may be used.

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US09/093,249 US6093236A (en) 1998-05-30 1998-06-08 Porous pellet adsorbents fabricated from nanocrystals
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