CA2167184C - Densified carbon black adsorbent and a process for adsorbing a gas with such an adsorbent - Google Patents
Densified carbon black adsorbent and a process for adsorbing a gas with such an adsorbent Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Abstract
The present invention discloses an adsorbent comprising a densified carbon black. The densified carbon black comprising the adsorbent preferably has an increase in density of from about 100 % to about 500 % above the undensified form of the adsorbent. The densified carbon black adsorbent has an increase in addition capacity per unit volume over the undensified form of the adsorbent in excess of 100 %. The densified carbon blacks are particularly useful as adsorbents for gases.
Description
W O 95/26812 2 1 6 7 1 8 4 PCTAUS9~/03806 DENSIFIED CARBON BLACK ADSORBENT AND A PROCESS
FOR ADSORBING A GAS WITH SUCH AN ADSORBFNT
BACKGROUND OF THE INVENTION
The present invention relates to an adsorbent comprising a densified carbon black, and a process for adsorbing a gas with such an adsorbent.
The adsorption of gases is an important component of many industrial processes. The extent of adsorption is dependent on the ability of the adsorbent to contain the gas. The effectiveness of an adsorbent may be judged from several 10 criteria, depending on the application. The adsorption capacity of the adsorbent may be expressed in terms of the adsorption per unit mass of the adsorbent, or in terms of the adsorption capacity per unit volume of the adsorbent. For some applications, such as the adsorptive storage of natural gas, space is a constraint, and so the adsorption capacity per unit volume of the adsorbent is the criterion for measuring its 15 effectiveness. Thus, a good adsorbent should have a high adsorption capacity both on a unit mass basis, as well as on a unit volume basis. The adsorption capacity per unit volume of adsorbent is dependent on the adsorption capacity per unit mass, as well as the bulk density of the adsorbent material. Thus, increasing the bulk density of the adsorbent will cause an increase in adsorption capacity per unit volume of the 20 adsorbent.
A number of carbon adsorbents have been invesliyat6d in the past. For example, Mullhaupt, et al., ~Carbon Adsorbents For Natural Gas Storage~, International Carbon Conference, June 21-26, 1992, discloses the use of active carbon as a methane adsorbent, as well as the use of certain carbon blacks as 25 methane adsorbents.
U.S. Patent No. 4,999,330 to Bose, ~!., describes a densified carbonaceous material for use as a methane adsorbent. As disclosed in this patent, while there is an increase in the density of the adsorbent of from 50% to 200%, the corresponding increase in the adsorption capacity per unit volume of the adsorbent 30 ranges from about 20% to about 100%.
It is, therefore, an object of the invention to provide a densified carbon black that exhibits an adsorption capacity per unit volume superior to that shown by undensified carbon blacks.
It is a further object of the invention to provide a process for using such a 35 densified carbon black as an adsorbent for gases.
FOR ADSORBING A GAS WITH SUCH AN ADSORBFNT
BACKGROUND OF THE INVENTION
The present invention relates to an adsorbent comprising a densified carbon black, and a process for adsorbing a gas with such an adsorbent.
The adsorption of gases is an important component of many industrial processes. The extent of adsorption is dependent on the ability of the adsorbent to contain the gas. The effectiveness of an adsorbent may be judged from several 10 criteria, depending on the application. The adsorption capacity of the adsorbent may be expressed in terms of the adsorption per unit mass of the adsorbent, or in terms of the adsorption capacity per unit volume of the adsorbent. For some applications, such as the adsorptive storage of natural gas, space is a constraint, and so the adsorption capacity per unit volume of the adsorbent is the criterion for measuring its 15 effectiveness. Thus, a good adsorbent should have a high adsorption capacity both on a unit mass basis, as well as on a unit volume basis. The adsorption capacity per unit volume of adsorbent is dependent on the adsorption capacity per unit mass, as well as the bulk density of the adsorbent material. Thus, increasing the bulk density of the adsorbent will cause an increase in adsorption capacity per unit volume of the 20 adsorbent.
A number of carbon adsorbents have been invesliyat6d in the past. For example, Mullhaupt, et al., ~Carbon Adsorbents For Natural Gas Storage~, International Carbon Conference, June 21-26, 1992, discloses the use of active carbon as a methane adsorbent, as well as the use of certain carbon blacks as 25 methane adsorbents.
U.S. Patent No. 4,999,330 to Bose, ~!., describes a densified carbonaceous material for use as a methane adsorbent. As disclosed in this patent, while there is an increase in the density of the adsorbent of from 50% to 200%, the corresponding increase in the adsorption capacity per unit volume of the adsorbent 30 ranges from about 20% to about 100%.
It is, therefore, an object of the invention to provide a densified carbon black that exhibits an adsorption capacity per unit volume superior to that shown by undensified carbon blacks.
It is a further object of the invention to provide a process for using such a 35 densified carbon black as an adsorbent for gases.
2 1 6 / 1 8 4 PCT/US95/03806 SUMMARY OF THE INVFNTION
The present invention meets these and other objects by providing new adsorbents comprising densified carbon blacks. Upon densification, the carbon blacks preferably have an increase in adsorption capacity per unit volume in excess of 100% or more, up to 400% or more, as compared to an undensified carbon black.
The "carbon black" referred to in this invention may be any carbon black, e.g., fumace black, thermal black, lamp black, acetylene black, or a carbon black manufactured by any other means, including carbon black that is formed as a by-product in a process whose primary product is not carbon black. Preferably, the 10 carbon black is a furnace carbon black.
The present invention also provides a process for adsorbing a gas with a densified carbon black adsorbent.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plot showing uniaxial densi~ication curves for a carbon black, CB-1, and an activated carbon having a nitrogen BET surface area (SA) of 2050 m2/g.
FIG. 2 is a plot showing the methane adsorption capacity per unit volume of undensified, isoslatically densified, and uniaxially densified carbon blacks.
DETAILED DESCRIPTION OF THE INVENTION
When densification is carried out on carbon black as described below, there is a substantial increase in adsGr~tiol~ capacity per unit volume of the carbon black. One important application of densified adsorbents is in the adsorptive storage of natural gas, the efficacy of the adsGrL,e,)l being measured by the adsorption25 capacity for methane, per unit volume of adsorbent, at a specified pressure and room temperature. The adsorption capacity per unit volume of adsorbent can be calculated by VV=(Vw)(d) where Vw is the adsorption capacity of the material per unit mass of adsorbent, and d 30 is the density of the adsorbent pellets. On densifying the material, the density d is increased, and so the adsorption capacity per unit volume, Vv, also increases.
The carbon black may be densified by any one of several densification techniques known in the prior art. One way of compressing the carbon black particles is by the application of pressure uniformly in all directions (isostatic densification ).
35 For example, the carbon black particles may be densified in a pin pelletizer. The pin pelletizer relies on capillary forces from a wetting fluid, (usually, but not necessarily, water) to densify the carbon black particles and form pellets. Typically, a measured quantity of water is added to a known quantity of carbon black in a pin pelletizer, and WO 95/26812 2 1 6 :~ ~ 8 4 PCT/US95/03806 the resulting mixture is agitated. The rolling motion of the pins and capillary forces due to the wetting fluid cause the formation of pellets.
Some other types of equipment which may be used for isostatic densification in the densification of carbon black include, but are not restricted to, 5 drum pelletizers and disc pelletizers. Operation of such equipment is well known to those skilled in the art, and particularly in the carbon black industry.
Another means of densificalion of carbon black is by application of pressure in one direction only (uniaxial densification ). This technique is commonly used in various fields e.g. catalysis and pharmaceuticals, among others. This may be 10 achieved, for example, by the following procedure. A known mass of carbon black is carefully loaded into a die. For the specific procedure considered here, a steel die of circular cross-section with an internal diameter of 0.5 inches was used. A plunger of the same external diameter as the internal diameter of the die is inserted into the die and the combination is inserted between the platens of a hydraulic press. Force is 15 applied on the plunger until the desired pressure is exerted on the carbon black within the die. For the present procedure, 0.4 gm of carbon black was subjected to a force of about 20,000 Ibs. (corresponding to a pressure greater than 100,000 psi in the .5 inch diameter die) for a period of three hours. At the end of the constant pressure period, the pressure is gradually reduced and the pellet removed from the die. The 20 volume of the pellet can be calculated from the height of pellet and the diameter of the die. From the weight and the volume, the density of the pellet may be calculated.
Table 1 lists several fumace carbon blacks studied for the purposes of demonstrating the present invention, along with the physical properties of theseblacks.
~ t 6 ~ 1 ~4 TABLE l: Propertties of some carbon blacks.
Furnace carbon DBP lodine No. CTAB BET
black N2S.A.
m2l9 BLACK PEARLS~
carbon black Carbon Black Analytical Properties The CTAB of the carbon blacks was determined according to ASTM Test Procedure D3765-85.
The iodine absorption number (l2No.) of the carbon blacks was determined according to ASTM Test Procedure D1510.
The nitrogen surface area (N2SA) of the carbon blacks was determined according to ASTM Test Procedure D3037-Method A.
The dibutyl phthalate absorption value (DBP) of the carbon was determined according to ASTM Test Procedure D3493-86.
For BLACK PEARLS~) 2000 furnace carbon black, manufactured and sold by Cabot Corporation, the density ranged bel~Jccn about 0.1 and 0.15 g/cm3 before densification, and this increased to between 0.27 g/cm3 and 0.3 g/cm3 after isost~tic densification in a pin pelletizer. The density attained by BLACK PEARLS~) 2000 carbon black after uniaxial densification, as described above, ranged between 0.45 and 0.6 g/cm3. Similarly, the density of another furnace black, designated herein W O 95/26812 PCTrUS9~/03806 as CB-1, before densification and after uniaxial densification, changed from between 0.1 and 0.15 g/cm3, to between 0.6 and 0.75 g/cm3, respectively.
FIG. 1 shows uniaxial densification curves for an activated carbon -powder having a nitrogen BET surface area of 2050 m2/gm (hereinafter the activated 5 carbon), and the CB-1 carbon black. Clearly, the activated carbon does not densify as well as the CB-1 carbon black. Though the initial density of the carbon black is lower than that of the activated carbon, the final density of the CB-1 carbon black at the end of the densification - decompression cycle is higher than that of the activated carbon.
Table 2 shows the condition of the two materials at various stages in the 10 uniaxial densification experiment. The percentage increase in density after densification is about 96% for the activated carbon, compared to an increase of greater than 400% for the CB-1 carbon black. It was observed that while the activated carbon did not retain any semblance of shape and became a powder almost immediately after removal from the die, the CB-1 carbon black retained a pellet shape 15 after removal from the die. The point to be noted here is that after decompression, the carbon black has a much higher density than exhibited by the activated carbon. Thus it may be assumed that the difference between the structures of the activated carbon and the carbon black is responsible for the inherently superior densification behavior of carbon black.
WO 95/26812 2 1 6 7 t 8 4 PCT/US95/03806 TABLE 2: Data from uniaxial densification experiment for activated carbon and CB-1 carbon black (numbers in brackets show the percentage increase over the undensified n,aterlal).
Stage in activated carbonCB-1 carbon black denslfication cycle Before loading material density = 0.3 g/cm3density = 0.14 g/cm3 into die Material in die before density = 0.42 g/cm3density = 0.25 g/cm3 densification begins [40%] [79%]
Maximum densification density = 1.23 g/cm3density = 1.33 g/cm3 (at 80,000 psi) [310%] [850%]
Material in die at the density = 0.59 g/cm3density = 0.72 g/cm3 end of densification [96%] [414%]
cycle Material removed from Does not retainCylindrically shaped die shape, crumbles into pellet is obtained powder Several specific non-limiting examples of gas adsorption are set forth in Examples I and ll. Examples I and ll describe the adsorption of nitrogen at 77 K, carbon dioxide at 273 K, methane at 298 K and butane at 273 K. These Examples, carried out with different gases under different conJitiol-s of temperature and 10 pressure, demonstrate the general applicability of densified carbon black as an adsorbent. Example lll demonstrates the use of several different densified carbon blacks as adsorbents to show that any carbon black can be densified as describedherein for use as an adsorbent. Thus, it should be understood that the invention is in no way restricted to the specific examples herein, and that the examples serve only to 15 illustrate the usefulness of the invention.
EXAMPLE 1-- Enhancement of the adsorption properties of BLACK
PEARLS~' 2000 carbon black through densification.
Table 3 shows the adsorption properties of BACK PEARLS~) 2000 carbon black as determined by the adsorption of various gases under different conditions of temperature and pressure, on a unit volume basis.
TABLE 3: Adsorption properties of undensified and densified BLACK
PEARLS~) 2000 carbon black per unit volume of material (numbers in brackets show the percentage incre-~e over the undensified "at~rial) Adsorption property Undensified Densified Densified per unit volume ("fluffy") isosotatically in uniaxially (cm3) carbon (Density = 0.12 a pin pelletizer (density = 0.6 g/cm3) (dens~ty = 0.29 g/cm3) g/cm3) BET surface area, m2/cm3 carbon 175.2 437 [149%]goo [414%]
Micropore volume, cm3/cm3 carbon 0.1158 0.2799 [142%[0.579 [400%]
Methane adsorption capacity at 298 K and 20 49 [145%]102 [410%]
35 atm., cm3 STP/cm3 carbon From the above Table 3, the following can be observed in connection with the ability of a densified carbon black to adsorb nitogen, carbon dioxide and methane gases:
1) BET surface area: The adsorption of nitrogen at 77 K is commonly used as a technique for determining the surface area of a carbon black. This may be done in accordance with ASTM Test Procedure D3037-Method A. The BET surface area is widely used by those skilled in the art as a criterion for judging the usefulness of a material as an adsorbent. The higher the BET surface area, the better the 15 adsorption qualities of the adsorbent for nitrogen at 77 K. The surface area may be expressed in m2/gm, or m2/cm3 of adsGrbe,lt. As stated previously, the objective here is to increase the surface area per unit volume of the adsorbent. Table 3 shows data for the BET surface area of BLACK PEARLS g~ 2000 carbon black before densification, and after densification using isostatic densi~ication or uniaxial densification. From the 20 data shown in Table 3 it is clear that the surface area per unit volume of the carbon black increases after densi~icatiGn. Thus the densi~icatio" process is highly beneficial to the adsorption properties of the carbon black, and shows that nitrogen is adsorbed in an increased amount.
WO 95/26812 2~ 1, 6 ~ PCT/US95/03806 2) Micropore volume from CO2 adsorption at 273 K: The adsorption of carbon dioxide at 273K is indicative of the adsorption behavior of gases that are close to their critical temperature. It is also possible to calculate the micropore volume of the carbon black by applying an adsorption theory to the carbon dioxide adsorption 5 data. In this instance, the micropore volume was determined using the method of Dubinin and Astakhov as found in M. M. Dubinin, Pro~ress in Surface and MembraneScience. Vol. 9, edited by Cadenhead, et al., Academic Press, New York (1975).
Table 3 shows the micropore volume per unit volume of carbon black, both before and after isostatic or uniaxial densification. It is clear from Table 3 that the micropore 10 volume available in a unit volume of adsorbent increases after densifying the carbon black. This indicates that the amount of CO2 adsorbed, per unit volume, is increased upon densification of the carbon black, since the quantity of CO2 adsorbed is directly proportional to the micropore volume.
The present invention meets these and other objects by providing new adsorbents comprising densified carbon blacks. Upon densification, the carbon blacks preferably have an increase in adsorption capacity per unit volume in excess of 100% or more, up to 400% or more, as compared to an undensified carbon black.
The "carbon black" referred to in this invention may be any carbon black, e.g., fumace black, thermal black, lamp black, acetylene black, or a carbon black manufactured by any other means, including carbon black that is formed as a by-product in a process whose primary product is not carbon black. Preferably, the 10 carbon black is a furnace carbon black.
The present invention also provides a process for adsorbing a gas with a densified carbon black adsorbent.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plot showing uniaxial densi~ication curves for a carbon black, CB-1, and an activated carbon having a nitrogen BET surface area (SA) of 2050 m2/g.
FIG. 2 is a plot showing the methane adsorption capacity per unit volume of undensified, isoslatically densified, and uniaxially densified carbon blacks.
DETAILED DESCRIPTION OF THE INVENTION
When densification is carried out on carbon black as described below, there is a substantial increase in adsGr~tiol~ capacity per unit volume of the carbon black. One important application of densified adsorbents is in the adsorptive storage of natural gas, the efficacy of the adsGrL,e,)l being measured by the adsorption25 capacity for methane, per unit volume of adsorbent, at a specified pressure and room temperature. The adsorption capacity per unit volume of adsorbent can be calculated by VV=(Vw)(d) where Vw is the adsorption capacity of the material per unit mass of adsorbent, and d 30 is the density of the adsorbent pellets. On densifying the material, the density d is increased, and so the adsorption capacity per unit volume, Vv, also increases.
The carbon black may be densified by any one of several densification techniques known in the prior art. One way of compressing the carbon black particles is by the application of pressure uniformly in all directions (isostatic densification ).
35 For example, the carbon black particles may be densified in a pin pelletizer. The pin pelletizer relies on capillary forces from a wetting fluid, (usually, but not necessarily, water) to densify the carbon black particles and form pellets. Typically, a measured quantity of water is added to a known quantity of carbon black in a pin pelletizer, and WO 95/26812 2 1 6 :~ ~ 8 4 PCT/US95/03806 the resulting mixture is agitated. The rolling motion of the pins and capillary forces due to the wetting fluid cause the formation of pellets.
Some other types of equipment which may be used for isostatic densification in the densification of carbon black include, but are not restricted to, 5 drum pelletizers and disc pelletizers. Operation of such equipment is well known to those skilled in the art, and particularly in the carbon black industry.
Another means of densificalion of carbon black is by application of pressure in one direction only (uniaxial densification ). This technique is commonly used in various fields e.g. catalysis and pharmaceuticals, among others. This may be 10 achieved, for example, by the following procedure. A known mass of carbon black is carefully loaded into a die. For the specific procedure considered here, a steel die of circular cross-section with an internal diameter of 0.5 inches was used. A plunger of the same external diameter as the internal diameter of the die is inserted into the die and the combination is inserted between the platens of a hydraulic press. Force is 15 applied on the plunger until the desired pressure is exerted on the carbon black within the die. For the present procedure, 0.4 gm of carbon black was subjected to a force of about 20,000 Ibs. (corresponding to a pressure greater than 100,000 psi in the .5 inch diameter die) for a period of three hours. At the end of the constant pressure period, the pressure is gradually reduced and the pellet removed from the die. The 20 volume of the pellet can be calculated from the height of pellet and the diameter of the die. From the weight and the volume, the density of the pellet may be calculated.
Table 1 lists several fumace carbon blacks studied for the purposes of demonstrating the present invention, along with the physical properties of theseblacks.
~ t 6 ~ 1 ~4 TABLE l: Propertties of some carbon blacks.
Furnace carbon DBP lodine No. CTAB BET
black N2S.A.
m2l9 BLACK PEARLS~
carbon black Carbon Black Analytical Properties The CTAB of the carbon blacks was determined according to ASTM Test Procedure D3765-85.
The iodine absorption number (l2No.) of the carbon blacks was determined according to ASTM Test Procedure D1510.
The nitrogen surface area (N2SA) of the carbon blacks was determined according to ASTM Test Procedure D3037-Method A.
The dibutyl phthalate absorption value (DBP) of the carbon was determined according to ASTM Test Procedure D3493-86.
For BLACK PEARLS~) 2000 furnace carbon black, manufactured and sold by Cabot Corporation, the density ranged bel~Jccn about 0.1 and 0.15 g/cm3 before densification, and this increased to between 0.27 g/cm3 and 0.3 g/cm3 after isost~tic densification in a pin pelletizer. The density attained by BLACK PEARLS~) 2000 carbon black after uniaxial densification, as described above, ranged between 0.45 and 0.6 g/cm3. Similarly, the density of another furnace black, designated herein W O 95/26812 PCTrUS9~/03806 as CB-1, before densification and after uniaxial densification, changed from between 0.1 and 0.15 g/cm3, to between 0.6 and 0.75 g/cm3, respectively.
FIG. 1 shows uniaxial densification curves for an activated carbon -powder having a nitrogen BET surface area of 2050 m2/gm (hereinafter the activated 5 carbon), and the CB-1 carbon black. Clearly, the activated carbon does not densify as well as the CB-1 carbon black. Though the initial density of the carbon black is lower than that of the activated carbon, the final density of the CB-1 carbon black at the end of the densification - decompression cycle is higher than that of the activated carbon.
Table 2 shows the condition of the two materials at various stages in the 10 uniaxial densification experiment. The percentage increase in density after densification is about 96% for the activated carbon, compared to an increase of greater than 400% for the CB-1 carbon black. It was observed that while the activated carbon did not retain any semblance of shape and became a powder almost immediately after removal from the die, the CB-1 carbon black retained a pellet shape 15 after removal from the die. The point to be noted here is that after decompression, the carbon black has a much higher density than exhibited by the activated carbon. Thus it may be assumed that the difference between the structures of the activated carbon and the carbon black is responsible for the inherently superior densification behavior of carbon black.
WO 95/26812 2 1 6 7 t 8 4 PCT/US95/03806 TABLE 2: Data from uniaxial densification experiment for activated carbon and CB-1 carbon black (numbers in brackets show the percentage increase over the undensified n,aterlal).
Stage in activated carbonCB-1 carbon black denslfication cycle Before loading material density = 0.3 g/cm3density = 0.14 g/cm3 into die Material in die before density = 0.42 g/cm3density = 0.25 g/cm3 densification begins [40%] [79%]
Maximum densification density = 1.23 g/cm3density = 1.33 g/cm3 (at 80,000 psi) [310%] [850%]
Material in die at the density = 0.59 g/cm3density = 0.72 g/cm3 end of densification [96%] [414%]
cycle Material removed from Does not retainCylindrically shaped die shape, crumbles into pellet is obtained powder Several specific non-limiting examples of gas adsorption are set forth in Examples I and ll. Examples I and ll describe the adsorption of nitrogen at 77 K, carbon dioxide at 273 K, methane at 298 K and butane at 273 K. These Examples, carried out with different gases under different conJitiol-s of temperature and 10 pressure, demonstrate the general applicability of densified carbon black as an adsorbent. Example lll demonstrates the use of several different densified carbon blacks as adsorbents to show that any carbon black can be densified as describedherein for use as an adsorbent. Thus, it should be understood that the invention is in no way restricted to the specific examples herein, and that the examples serve only to 15 illustrate the usefulness of the invention.
EXAMPLE 1-- Enhancement of the adsorption properties of BLACK
PEARLS~' 2000 carbon black through densification.
Table 3 shows the adsorption properties of BACK PEARLS~) 2000 carbon black as determined by the adsorption of various gases under different conditions of temperature and pressure, on a unit volume basis.
TABLE 3: Adsorption properties of undensified and densified BLACK
PEARLS~) 2000 carbon black per unit volume of material (numbers in brackets show the percentage incre-~e over the undensified "at~rial) Adsorption property Undensified Densified Densified per unit volume ("fluffy") isosotatically in uniaxially (cm3) carbon (Density = 0.12 a pin pelletizer (density = 0.6 g/cm3) (dens~ty = 0.29 g/cm3) g/cm3) BET surface area, m2/cm3 carbon 175.2 437 [149%]goo [414%]
Micropore volume, cm3/cm3 carbon 0.1158 0.2799 [142%[0.579 [400%]
Methane adsorption capacity at 298 K and 20 49 [145%]102 [410%]
35 atm., cm3 STP/cm3 carbon From the above Table 3, the following can be observed in connection with the ability of a densified carbon black to adsorb nitogen, carbon dioxide and methane gases:
1) BET surface area: The adsorption of nitrogen at 77 K is commonly used as a technique for determining the surface area of a carbon black. This may be done in accordance with ASTM Test Procedure D3037-Method A. The BET surface area is widely used by those skilled in the art as a criterion for judging the usefulness of a material as an adsorbent. The higher the BET surface area, the better the 15 adsorption qualities of the adsorbent for nitrogen at 77 K. The surface area may be expressed in m2/gm, or m2/cm3 of adsGrbe,lt. As stated previously, the objective here is to increase the surface area per unit volume of the adsorbent. Table 3 shows data for the BET surface area of BLACK PEARLS g~ 2000 carbon black before densification, and after densification using isostatic densi~ication or uniaxial densification. From the 20 data shown in Table 3 it is clear that the surface area per unit volume of the carbon black increases after densi~icatiGn. Thus the densi~icatio" process is highly beneficial to the adsorption properties of the carbon black, and shows that nitrogen is adsorbed in an increased amount.
WO 95/26812 2~ 1, 6 ~ PCT/US95/03806 2) Micropore volume from CO2 adsorption at 273 K: The adsorption of carbon dioxide at 273K is indicative of the adsorption behavior of gases that are close to their critical temperature. It is also possible to calculate the micropore volume of the carbon black by applying an adsorption theory to the carbon dioxide adsorption 5 data. In this instance, the micropore volume was determined using the method of Dubinin and Astakhov as found in M. M. Dubinin, Pro~ress in Surface and MembraneScience. Vol. 9, edited by Cadenhead, et al., Academic Press, New York (1975).
Table 3 shows the micropore volume per unit volume of carbon black, both before and after isostatic or uniaxial densification. It is clear from Table 3 that the micropore 10 volume available in a unit volume of adsorbent increases after densifying the carbon black. This indicates that the amount of CO2 adsorbed, per unit volume, is increased upon densification of the carbon black, since the quantity of CO2 adsorbed is directly proportional to the micropore volume.
3) Adsorption of methane at 298K: One of the important future application for adsorbents is the use of such adsorbents to store natural gas for automobiles and other applications. The usefulness of the adsorbent stems from the fact that the same quantity of natural gas that is stored in a tank devoid of adsorbent at high pressures, on the order of 3000 psi, can be stored at considerably lower 20 pressures in the range of 500-1000 psi by utilizing a tank filled with adsorbent. To gauge the suitability of an adsorbent for the storage of natural gas, the adsorption of methane is commonly carried out in the laboratory. Since natural gas consists primarily of methane, the adsorption capacity of methane can be used to gauge the performance of the adsorbent for natural gas storage applications.
Densification of the adsorbent assumes great importance for natural gas appl.-~tions because the usefulness of the adsorbent is determined by measuring the quantity of methane that can be delivered by the adsorbent, per unit volume of the storage tank. The higher the density of the adsorbent, the smaller the volume of the storage tank required to accommodate a particular mass of adsorbent. Thus, if two materials have the same adsorption c~p~city for methane per unit weight of the adsG,b6nt (i.e. they have the same specific adsorption), the material with a higher density will have a higher adsorption capacity per unit volume of adsorbent.
FIG. 2 shows methane adsorption isotherms at room temperature for BLACK PEARLS(~) 2000 carbon black based on unit volume of adsorbent for the undensified black with a density of 0.12 g/cm3, the black isostatically densified in a pin pelletizer with a density of 0.29 g/cm3, and the black densified by uniaxial densification, with a density of 0.6 g/cm3. As illustrated in FIG. 2, the adsorption c~p~city per unit volume of the densified carbon black increases substantially over that of the undensified carbon black. It is therefore clear that the increase in density of the carbon black as described herein, translates directly into an increase in adsorption c~p~city per unit volume of the adsorbent.
5 Example ll-- Adsorption of butane on CB-1 carbon black at 273 K:
The adsorption of butane at 273K was carried out on the CB-1 carbon black to establish the suitability of densified carbon blacks for the adsorption of larger gas molecules, such as normal alkanes. The quantity of butane adsorbed at a 10 pressure of 549 Torr was used as a measure of the effectiveness of the CB-1 black as an adsorbent for larger gas molecules. Table 4 shows the change in adsorption c~p~city of the CB-1 black per unit volume of adsorbent, before densification and after uniaxial densification. As the data set forth in Table 4 clearly show, the adsorption c~p~city for butane per unit volume of the adsorbent increases after densification.
Table 4: Adsorption ca~,acil~ of CB-1 carbon black for butane, before and after densification (numbers in brackets show the percentage increase over the undensified material) Adsorption property per Undensified Densified uniaxially unit volume (cm3) carboa ("fluffy") (density = 0.72 g/cm3) (density = 0.14 g/cm3) Butane adsorption capacity of CB-1 at 549 34 184 [441 %
Torr and O C, cm3STP/cm3carbon Example lll Adsorption of gases on dillerent types of undensified and densified carbon blacks:
Example lll considers the adsorption of gases on several different carbon blacks before and after densilicatiGn to show that the present invention is applicable to using any densified carbon black as an adsorbent.
Table 5 shows the BET surface areas as determined from nitrogen adsorption at 77 K, for several carbon blacks. Table 5 shows the BET surface area WO 95/26812 2 t h 7 t ~ ~ PCT/US95/03806 per unit volume, before and after densification. The BET surface area per unit volume of all the carbon blacks listed in Table 5 show significant increases after densification.
Table 5: BET surface area for various densified and undensified carbon 5 blacks (numbers in brackets show the perc~.,tage increase over the undensified material) Carbon blackBET surface area, BET surface area, m2/cm3, carbon, m2/cm3, carbon, undensified densified uniaxially BLACK PEARLS~ 175 900 [414%]
2000 (density = 0.12 g/cm3) (density = 0.6 g/cm3) carbon black CB-1 260 1289 [396%]
(density = 0.12 g/cm3) (density = 0.72 g/cm3) CB-4 183 1037 [467%l (density = 0.1 g/cm3) (density = 0.57 g/cm3) Table 6 presents data showing the methane adsorption capacities per 10 unit volume of various carbon blacks, at a temperature of 298 K, and 35 atm.
pressure. The data show the adsorption c~p~cities on a unit volume basis, both before and after densilication. As the data set forth in Table 6 show, there is a large increase in the adsorption capacity per unit volume of each of the densified carbon blacks over the undensified carbon blacks.
2 1 ~7 1 84 WO 95/26812 . PCT/US95/03806 Table 6: Melhalle adsorption capacities per unit volume of various carbon blacks, lefore and after densification (numbers in brackets show the. percentage increase.over the undensified material) arbon black Methane adsorption Methane adsorption capacity, cm3STP/cm3 capacity, cm3STP/cm3 carbon for undensified carbon for uniaxially material densified material BLACK PEARLS(~) 20 102 [410%]
2000 (density = 0.12 g/cm3)(density = 0.6 g/cm3) carbon black CB-1 22 115 [423%]
(density = 0.14 g/cm3)(density = 0.72 g/cm3) CB-2 20 102 [410%]
(density = 0.12 g/cm3)(density = 0.61 g/cm3) CB-3 17 95 [459%]
(density = 0.1 g/cm3)(density = 0.55 g/cm3) CB-4 18 105 [483%]
(density = 0.1 g/cm3) (density = 0.57 g/cm3) Expressed in other units, Table 7 shows the methane adsorption c~p~city of BLACK PEARLS~) 2000 carbon black before and after densification. Thegas storage capacity, as shown in Table 7, clearly increases by an amount of from 142 % to 402 % after densification of the carbon black either by isostatic or uniaxial 1 0 densification.
WO 95/26812 f t ~ $ 4 PCT/US95/03806 Table 7: The effect of densification on methane storage ~ap~city (at 4Mpa and 298 K of BLACK PEARLS(E) 2000 carbon black Adsorbent Density, Specific Storage g/cm3 adsorption, capacity, g CH4/100 9 9 CH4/l adsorbent adsorbent Undensified ("fluffy") 0.12 10.7 12.8 Isostatically densified in a pin 0.29 10.7 31 pelletizer (142%) Uniaxially densified to 100,000 psi 0.6 10.7 64.2 (402%) The purpose of the above examples and the data set forth in the associated tables was to demonstrate the superiority of utilizing the densified carbon blacks as adsorbents. Whereas known prior art carbonaceous materials, when densified, are characterized by an increase in adsorption capacity per unit volume of up to 100%, the densified carbon blacks of the present invention show an increase in adsorption capacity for a gas per unit volume of the adsorbent in excess of 100 % or more, and reach values of as much as 400 % or more, as compared to undensified carbon blacks. The examples provided herein demonstrate the adsorption of various gases on a range of carbon blacks, under various conditions, to show that the present invention is applicable to any carbon black for the adsorption of any gas.
While preferred embodiments have been shown and described, various modifications and substitutions may be made without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of example and not by limitation.
Densification of the adsorbent assumes great importance for natural gas appl.-~tions because the usefulness of the adsorbent is determined by measuring the quantity of methane that can be delivered by the adsorbent, per unit volume of the storage tank. The higher the density of the adsorbent, the smaller the volume of the storage tank required to accommodate a particular mass of adsorbent. Thus, if two materials have the same adsorption c~p~city for methane per unit weight of the adsG,b6nt (i.e. they have the same specific adsorption), the material with a higher density will have a higher adsorption capacity per unit volume of adsorbent.
FIG. 2 shows methane adsorption isotherms at room temperature for BLACK PEARLS(~) 2000 carbon black based on unit volume of adsorbent for the undensified black with a density of 0.12 g/cm3, the black isostatically densified in a pin pelletizer with a density of 0.29 g/cm3, and the black densified by uniaxial densification, with a density of 0.6 g/cm3. As illustrated in FIG. 2, the adsorption c~p~city per unit volume of the densified carbon black increases substantially over that of the undensified carbon black. It is therefore clear that the increase in density of the carbon black as described herein, translates directly into an increase in adsorption c~p~city per unit volume of the adsorbent.
5 Example ll-- Adsorption of butane on CB-1 carbon black at 273 K:
The adsorption of butane at 273K was carried out on the CB-1 carbon black to establish the suitability of densified carbon blacks for the adsorption of larger gas molecules, such as normal alkanes. The quantity of butane adsorbed at a 10 pressure of 549 Torr was used as a measure of the effectiveness of the CB-1 black as an adsorbent for larger gas molecules. Table 4 shows the change in adsorption c~p~city of the CB-1 black per unit volume of adsorbent, before densification and after uniaxial densification. As the data set forth in Table 4 clearly show, the adsorption c~p~city for butane per unit volume of the adsorbent increases after densification.
Table 4: Adsorption ca~,acil~ of CB-1 carbon black for butane, before and after densification (numbers in brackets show the percentage increase over the undensified material) Adsorption property per Undensified Densified uniaxially unit volume (cm3) carboa ("fluffy") (density = 0.72 g/cm3) (density = 0.14 g/cm3) Butane adsorption capacity of CB-1 at 549 34 184 [441 %
Torr and O C, cm3STP/cm3carbon Example lll Adsorption of gases on dillerent types of undensified and densified carbon blacks:
Example lll considers the adsorption of gases on several different carbon blacks before and after densilicatiGn to show that the present invention is applicable to using any densified carbon black as an adsorbent.
Table 5 shows the BET surface areas as determined from nitrogen adsorption at 77 K, for several carbon blacks. Table 5 shows the BET surface area WO 95/26812 2 t h 7 t ~ ~ PCT/US95/03806 per unit volume, before and after densification. The BET surface area per unit volume of all the carbon blacks listed in Table 5 show significant increases after densification.
Table 5: BET surface area for various densified and undensified carbon 5 blacks (numbers in brackets show the perc~.,tage increase over the undensified material) Carbon blackBET surface area, BET surface area, m2/cm3, carbon, m2/cm3, carbon, undensified densified uniaxially BLACK PEARLS~ 175 900 [414%]
2000 (density = 0.12 g/cm3) (density = 0.6 g/cm3) carbon black CB-1 260 1289 [396%]
(density = 0.12 g/cm3) (density = 0.72 g/cm3) CB-4 183 1037 [467%l (density = 0.1 g/cm3) (density = 0.57 g/cm3) Table 6 presents data showing the methane adsorption capacities per 10 unit volume of various carbon blacks, at a temperature of 298 K, and 35 atm.
pressure. The data show the adsorption c~p~cities on a unit volume basis, both before and after densilication. As the data set forth in Table 6 show, there is a large increase in the adsorption capacity per unit volume of each of the densified carbon blacks over the undensified carbon blacks.
2 1 ~7 1 84 WO 95/26812 . PCT/US95/03806 Table 6: Melhalle adsorption capacities per unit volume of various carbon blacks, lefore and after densification (numbers in brackets show the. percentage increase.over the undensified material) arbon black Methane adsorption Methane adsorption capacity, cm3STP/cm3 capacity, cm3STP/cm3 carbon for undensified carbon for uniaxially material densified material BLACK PEARLS(~) 20 102 [410%]
2000 (density = 0.12 g/cm3)(density = 0.6 g/cm3) carbon black CB-1 22 115 [423%]
(density = 0.14 g/cm3)(density = 0.72 g/cm3) CB-2 20 102 [410%]
(density = 0.12 g/cm3)(density = 0.61 g/cm3) CB-3 17 95 [459%]
(density = 0.1 g/cm3)(density = 0.55 g/cm3) CB-4 18 105 [483%]
(density = 0.1 g/cm3) (density = 0.57 g/cm3) Expressed in other units, Table 7 shows the methane adsorption c~p~city of BLACK PEARLS~) 2000 carbon black before and after densification. Thegas storage capacity, as shown in Table 7, clearly increases by an amount of from 142 % to 402 % after densification of the carbon black either by isostatic or uniaxial 1 0 densification.
WO 95/26812 f t ~ $ 4 PCT/US95/03806 Table 7: The effect of densification on methane storage ~ap~city (at 4Mpa and 298 K of BLACK PEARLS(E) 2000 carbon black Adsorbent Density, Specific Storage g/cm3 adsorption, capacity, g CH4/100 9 9 CH4/l adsorbent adsorbent Undensified ("fluffy") 0.12 10.7 12.8 Isostatically densified in a pin 0.29 10.7 31 pelletizer (142%) Uniaxially densified to 100,000 psi 0.6 10.7 64.2 (402%) The purpose of the above examples and the data set forth in the associated tables was to demonstrate the superiority of utilizing the densified carbon blacks as adsorbents. Whereas known prior art carbonaceous materials, when densified, are characterized by an increase in adsorption capacity per unit volume of up to 100%, the densified carbon blacks of the present invention show an increase in adsorption capacity for a gas per unit volume of the adsorbent in excess of 100 % or more, and reach values of as much as 400 % or more, as compared to undensified carbon blacks. The examples provided herein demonstrate the adsorption of various gases on a range of carbon blacks, under various conditions, to show that the present invention is applicable to any carbon black for the adsorption of any gas.
While preferred embodiments have been shown and described, various modifications and substitutions may be made without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of example and not by limitation.
Claims (31)
1. An adsorbent comprising a densified carbon black, having a methane storage capacity increase per unit volume at 298ÀK and 35 atm of at least about 142% compared to an undensified carbon black.
2. The adsorbent of claim 1, wherein the densified carbon black has an increase in density of from about 100% to about 500% over the undensified carbon black.
3. The adsorbent of claim 1, wherein the densified carbon black has a nitrogen surface area of at least about 600 m2 /g.
4. The adsorbent of claim 1, wherein the densified carbon black has a DBP of at least about 150 cc/100 g.
5. The adsorbent of claim 1, wherein the densified carbon black has a bulk density of at least about 0.3 g/cm3.
6. The adsorbent of claim 1, wherein the densified carbon black has a micropore volume per cm3 of carbon increase determined by CO2 adsorption at 273ÀK over the undensified carbon black of at least about 142%.
7. The adsorbent of claim 1, wherein the densified carbon black is a densified furnace carbon black.
8. The adsorbent of claim 1, wherein the adsorbent is an adsorbent for a gas.
9. The adsorbent of claim 8 wherein the gas comprises methane, butane, nitrogen, or carbon dioxide.
10. The adsorbent of claim 9 wherein the gas is methane.
11. The adsorbent of claim 1, wherein the densified carbon black has an increase in density of from about 100% to about 500% over the undensified carbon black, a nitrogen surface area of at least about 600 m2/g, and a DBP of at least about 150 cc/100 g.
12. The adsorbent of claim 11, wherein the densified carbon black has an increase in methane adsorption per cm3 of carbon at 35 atm and 298ÀK over the undensified carbon black of at least about 145%.
13. A process for adsorbing a gas with an adsorbent comprising a densified carbon black, said process comprising the step of contacting said gas with said adsorbent for a sufficient time to adsorb at least a portion of said gas, and wherein said adsorbent has a methane storage capacity increase per unit volume at 298ÀK and 35 atm of at least about 142% compared to an undensified carbon black.
14. The process of claim 13, wherein the densified carbon black has an increase in density of from about 100% to about 500% over the undensified carbon black.
15. The process of claim 13, wherein the densified carbon black has a nitrogen surface area of at least about 600 m2/g.
16. The process of claim 13, wherein the densified carbon black has a DBP of at least about 150 cc/100 g.
17. The process of claim 13, wherein the densified carbon black has a bulk density of at least about 0.3 g/cm3.
18. The process of claim 13, wherein the densified carbon black has an increase in methane adsorption per cm3 of carbon at 298ÀK and 35 atm over the undensified carbon black of at least about 145%.
19. The process of claim 13, wherein the densified carbon black comprises a densified furnace carbon black.
20. The process of claim 13, wherein the gas comprises methane, butane, nitrogen, or carbon dioxide.
21. The process of claim 20 wherein the gas is methane.
22. The process of claim 13, wherein the densified carbon black has an increase in density of from about 100% to about 500% over the undensified carbon black, a nitrogen surface area of at least about 600 m2/g, and a DBP of at least about 150 cc/100 g.
23. The adsorbent of claim 1, wherein said densified carbon black has a methane storage capacity increase of from about 142% to about 402%
compared to an undensified carbon black.
compared to an undensified carbon black.
24. The adsorbent of claim 1, wherein said adsorbent has an increase in methane adsorption per cm3 of carbon at 298ÀK and 35 and of at least about 145% compared to an undensified carbon black.
25. The adsorbent of claim 24, wherein said adsorbent has a increase in methane adsorption per cm3 of carbon at 298ÀK and 35 atm of from about 145% to about 483% compared to an undensified carbon black.
26. The process of claim 13, wherein said adsorbent has a methane storage capacity increase of from about 142% to about 402% compared to an undensified carbon black.
27. An adsorbent consisting essentially of a densified carbon black.
28. The adsorbent of claim 27, wherein said densified carbon black has a density of at least about 0.29 g/cm3.
29. The adsorbent of claim 27, wherein the densified carbon black has a nitrogen surface area of at least about 600 m2/g.
30. A process for adsorbing a gas with an adsorbent consisting essentially of a densified carbon black, said process comprising the step of contacting said gas with said adsorbent for a sufficient time to adsorb at least a portion of said gas.
31. A process of claim 30, wherein said densified carbon black has a density of at least about 0.29 g/cm3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22283094A | 1994-04-05 | 1994-04-05 | |
| US08/222,830 | 1994-04-05 | ||
| PCT/US1995/003806 WO1995026812A1 (en) | 1994-04-05 | 1995-03-28 | Densified carbon black adsorbent and a process for adsorbing a gas with such an adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2167184A1 CA2167184A1 (en) | 1995-10-12 |
| CA2167184C true CA2167184C (en) | 2002-02-26 |
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| CA002167184A Expired - Fee Related CA2167184C (en) | 1994-04-05 | 1995-03-28 | Densified carbon black adsorbent and a process for adsorbing a gas with such an adsorbent |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0701478A1 (en) |
| CN (1) | CN1095688C (en) |
| AU (1) | AU688491B2 (en) |
| BR (1) | BR9506142A (en) |
| CA (1) | CA2167184C (en) |
| WO (1) | WO1995026812A1 (en) |
| ZA (1) | ZA952769B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO982245L (en) * | 1998-05-14 | 1999-11-15 | Kvaerner Tech & Res Ltd | Gas storage device |
| US6645287B2 (en) † | 2001-04-27 | 2003-11-11 | Cabot Corporation | Coating compositions comprising high t-area carbon products |
| DE102007050971B4 (en) * | 2007-03-14 | 2014-12-31 | BLüCHER GMBH | Process for the preparation of high performance adsorbents based on activated carbon with high meso- and macroporosity, high performance adsorbents and their use |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2843874A (en) * | 1954-07-26 | 1958-07-22 | Phillips Petroleum Co | Process and apparatus for densifying and pelleting carbon black |
| US4081370A (en) * | 1976-05-20 | 1978-03-28 | American Cyanamid Company | Use of carbon particulates with controlled density as adsorbents |
| EP0218403B1 (en) * | 1985-10-03 | 1992-12-09 | Calgon Carbon Corporation | Method and means for improved gas adsorption |
| US4999330A (en) * | 1988-03-22 | 1991-03-12 | Universite Du Quebec A Trois-Rivieres | High-density adsorbent and method of producing same |
| DE3908022C1 (en) * | 1988-09-23 | 1990-03-29 | Degussa Ag, 6000 Frankfurt, De | |
| US5292707A (en) * | 1992-11-25 | 1994-03-08 | Allied-Signal Inc. | Improving the density of carbon molecular sieves for the storage of natural gas |
-
1995
- 1995-03-28 EP EP95915428A patent/EP0701478A1/en not_active Withdrawn
- 1995-03-28 AU AU22310/95A patent/AU688491B2/en not_active Ceased
- 1995-03-28 BR BR9506142A patent/BR9506142A/en not_active IP Right Cessation
- 1995-03-28 WO PCT/US1995/003806 patent/WO1995026812A1/en not_active Application Discontinuation
- 1995-03-28 CA CA002167184A patent/CA2167184C/en not_active Expired - Fee Related
- 1995-03-28 CN CN95190498A patent/CN1095688C/en not_active Expired - Fee Related
- 1995-04-04 ZA ZA952769A patent/ZA952769B/en unknown
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| Publication number | Publication date |
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| BR9506142A (en) | 1996-03-12 |
| AU2231095A (en) | 1995-10-23 |
| CA2167184A1 (en) | 1995-10-12 |
| AU688491B2 (en) | 1998-03-12 |
| ZA952769B (en) | 1996-01-05 |
| EP0701478A1 (en) | 1996-03-20 |
| CN1095688C (en) | 2002-12-11 |
| WO1995026812A1 (en) | 1995-10-12 |
| CN1128962A (en) | 1996-08-14 |
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