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WO1995026812A1 - Adsorbant a base de noir de carbone densifie et procede d'adsorption d'un gaz au moyen d'un tel adsorbant - Google Patents

Adsorbant a base de noir de carbone densifie et procede d'adsorption d'un gaz au moyen d'un tel adsorbant Download PDF

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Publication number
WO1995026812A1
WO1995026812A1 PCT/US1995/003806 US9503806W WO9526812A1 WO 1995026812 A1 WO1995026812 A1 WO 1995026812A1 US 9503806 W US9503806 W US 9503806W WO 9526812 A1 WO9526812 A1 WO 9526812A1
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WO
WIPO (PCT)
Prior art keywords
adsorbent
carbon black
densified
density
densification
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.)
Ceased
Application number
PCT/US1995/003806
Other languages
English (en)
Inventor
Ralph Ulrich Boes
Douglas M. Smith
Ranjan Ghosal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cabot Corp
Original Assignee
Cabot Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cabot Corp filed Critical Cabot Corp
Priority to EP95915428A priority Critical patent/EP0701478A1/fr
Priority to BR9506142A priority patent/BR9506142A/pt
Priority to US08/591,607 priority patent/US5972826A/en
Priority to CA002167184A priority patent/CA2167184C/fr
Priority to AU22310/95A priority patent/AU688491B2/en
Publication of WO1995026812A1 publication Critical patent/WO1995026812A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes

Definitions

  • 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 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 effectiveness.
  • 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.
  • increasing the bulk density of the adsorbent will cause an increase in adsorption capacity per unit volume of the adsorbent.
  • U.S. Patent No. 4,999,330 to Bose, et al.. 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 ranges from about 20% to about 100%.
  • 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.
  • adsorbent comprising densified carbon blacks.
  • the 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., furnace 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.
  • the carbon black is a furnace carbon black.
  • the present invention also provides a process for adsorbing a gas with a densified carbon black adsorbent.
  • FIG. 1 is a plot showing uniaxial densification curves for a carbon black
  • FIG. 2 is a plot showing the methane adsorption capacity per unit volume of undensified, isostatically densified, and uniaxially densified carbon blacks.
  • densification When densification is carried out on carbon black as described below, there is a substantial increase in adsorption 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 adsorbent being measured by the adsorption 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 (V w )(d) where Vw is the adsorption capacity of the material per unit mass of adsorbent, and d 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 ).
  • 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 density the carbon black particles and form pellets.
  • a measured quantity of water is added to a known quantity of carbon black in a pin pelletizer, and 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, 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 densification 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 achieved, for example, by the following procedure.
  • a known mass of carbon black is carefully loaded into a die.
  • 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 applied on the plunger until the desired pressure is exerted on the carbon black within the die.
  • Table 1 lists several furnace carbon blacks studied for the purposes of demonstrating the present invention, along with the physical properties of these blacks.
  • the CTAB of the carbon blacks was determined according to ASTM Test
  • the iodine absorption number (I2N0.) of the carbon blacks was determined according to ASTM Test Procedure D1510.
  • N2SA nitrogen surface area
  • the dibutyl phthalate absorption value (DBP) of the carbon was determined according to ASTM Test Procedure D3493-86.
  • the density ranged between about 0.1 and 0.15 g/cm 3 before densification , and this increased to between 0.27 g/cm 3 and 0.3 g/cm 3 after isostatic densification in a pin pelletizer.
  • the density of another furnace black, designated herein as CB-1 before densification and after uniaxial densification , changed from between 0.1 and 0.15 g/cm 3 , to between 0.6 and 0.75 g/cm 3 , respectively.
  • FIG. 1 shows uniaxial densification curves for an activated carbon powder having a nitrogen BET surface area of 2050 m 2 /gm (hereinafter the activated carbon), and the CB-1 carbon black.
  • the activated carbon does not density as well as the CB-1 carbon black.
  • Table 2 shows the condition of the two materials at various stages in the 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.
  • Examples I and II 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 conditions of temperature and pressure, demonstrate the general applicability of densified carbon black as an adsorbent.
  • Example III demonstrates the use of several different densified carbon blacks as adsorbents to show that any carbon black can be densified as described herein for use as an adsorbent.
  • the invention is in no way restricted to the specific examples herein, and that the examples serve only to illustrate the usefulness of the invention.
  • 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 increase over the undensified material)
  • 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 adsorption qualities of the adsorbent for nitrogen at 77°K.
  • the surface area may be expressed in m 2 /gm, or m 2 /cm 3 of adsorbent. 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® 2000 carbon black before densification, and after densification using isostatic densification or uniaxial densification. From the data shown in Table 3 it is clear that the surface area per unit volume of the carbon black increases after densification. Thus the densification process is highly beneficial to the adsorption properties of the carbon black, and shows that nitrogen is adsorbed in an increased amount.
  • Micropore volume from C02 adsorption at 273°K The adsorption of carbon dioxide at 273°K 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 data.
  • micropore volume was determined using the method of Dubinin and Astakhov as found in M. M. Dubinin, Progress in Surface and Membrane Science. 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 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.
  • Adsorption of methane at 298°K 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 pressures in the range of 500-1000 psi by utilizing a tank filled with adsorbent.
  • the adsorption of methane is commonly carried out in the laboratory.
  • 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 applications 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 capacity for methane per unit weight of the adsorbent (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/cm 3 , the black isostatically densified in a pin pelletizer with a density of 0.29 g/cm 3 , and the black densified by uniaxial densification, with a density of 0.6 g/cm3.
  • the adsorption capacity 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 capacity per unit volume of the adsorbent.
  • Example III Adsorption of gases on different types of undensified and densified carbon blacks:
  • Example III considers the adsorption of gases on several different carbon blacks before and after densification 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 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 6 presents data showing the methane adsorption capacities per unit volume of various carbon blacks, at a temperature of 298°K, and 35 atm. pressure.
  • the data show the adsorption capacities on a unit volume basis, both before and after densification. 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.
  • Table 7 shows the methane adsorption capacity of BLACK PEARLS® 2000 carbon black before and after densification.
  • the gas 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 densification.
  • Table 7 The effect of densification on methane storage capacity (at 4Mpa and 298°K of BLACK PEARLS® 2000 carbon black

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention se rapporte à un adsorbant comprenant du noir de carbone densifié. Ce noir de carbone densifié présente de préférence un accroissement de densité de l'ordre d'environ 100 % à environ 500 % par rapport à la forme non densifiée de l'adsorbant. Ledit adsorbant présente une augmentation de capacité d'adsorption par volume unitaire supérieure à 100 % par rapport à la forme non densifiée de l'adsorbant. De tels noirs de carbone densifiés sont particulièrement aptes à être utilisés comme adsorbants pour les gaz.
PCT/US1995/003806 1994-04-05 1995-03-28 Adsorbant a base de noir de carbone densifie et procede d'adsorption d'un gaz au moyen d'un tel adsorbant Ceased WO1995026812A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP95915428A EP0701478A1 (fr) 1994-04-05 1995-03-28 Adsorbant a base de noir de carbone densifie et procede d'adsorption d'un gaz au moyen d'un tel adsorbant
BR9506142A BR9506142A (pt) 1994-04-05 1995-03-28 Adsorvente e processo para adsorver gás
US08/591,607 US5972826A (en) 1995-03-28 1995-03-28 Densified carbon black adsorbent and a process for adsorbing a gas with such an adsorbent
CA002167184A CA2167184C (fr) 1994-04-05 1995-03-28 Adsorbant a base de noir de carbone densifie et procede d'adsorption d'un gaz au moyen d'un tel adsorbant
AU22310/95A AU688491B2 (en) 1994-04-05 1995-03-28 Densified carbon black adsorbent and a process for adsorbing a gas with such an adsorbent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US22283094A 1994-04-05 1994-04-05
US08/222,830 1994-04-05

Publications (1)

Publication Number Publication Date
WO1995026812A1 true WO1995026812A1 (fr) 1995-10-12

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EP (1) EP0701478A1 (fr)
CN (1) CN1095688C (fr)
AU (1) AU688491B2 (fr)
BR (1) BR9506142A (fr)
CA (1) CA2167184C (fr)
WO (1) WO1995026812A1 (fr)
ZA (1) ZA952769B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999058627A3 (fr) * 1998-05-14 2000-01-20 Kvaerner Tech & Res Ltd Procede d'utilisation d'un materiau de base
EP1406976B2 (fr) † 2001-04-27 2021-07-07 Cabot Corporation Compositions de revetement contenant des produits de carbone a grande surface t

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007050971B4 (de) * 2007-03-14 2014-12-31 BLüCHER GMBH Verfahren zur Herstellung von Hochleistungsadsorbentien auf der Basis von Aktivkohle mit hoher Meso- und Makroporosität, Hochleistungsadsorbentien und deren Verwendung

Citations (5)

* Cited by examiner, † Cited by third party
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
EP0218403A2 (fr) * 1985-10-03 1987-04-15 Calgon Carbon Corporation Procédé et moyen d'adsorption d'un gaz
EP0360236A2 (fr) * 1988-09-23 1990-03-28 Degussa Aktiengesellschaft Procédé de fabrication à sec de perles de noir de carbone et dispositif pour un mode de mise en oeuvre du procédé
US5292707A (en) * 1992-11-25 1994-03-08 Allied-Signal Inc. Improving the density of carbon molecular sieves for the storage of natural gas

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4999330A (en) * 1988-03-22 1991-03-12 Universite Du Quebec A Trois-Rivieres High-density adsorbent and method of producing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
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
EP0218403A2 (fr) * 1985-10-03 1987-04-15 Calgon Carbon Corporation Procédé et moyen d'adsorption d'un gaz
EP0360236A2 (fr) * 1988-09-23 1990-03-28 Degussa Aktiengesellschaft Procédé de fabrication à sec de perles de noir de carbone et dispositif pour un mode de mise en oeuvre du procédé
US5292707A (en) * 1992-11-25 1994-03-08 Allied-Signal Inc. Improving the density of carbon molecular sieves for the storage of natural gas

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999058627A3 (fr) * 1998-05-14 2000-01-20 Kvaerner Tech & Res Ltd Procede d'utilisation d'un materiau de base
EP1406976B2 (fr) † 2001-04-27 2021-07-07 Cabot Corporation Compositions de revetement contenant des produits de carbone a grande surface t

Also Published As

Publication number Publication date
BR9506142A (pt) 1996-03-12
CN1128962A (zh) 1996-08-14
AU688491B2 (en) 1998-03-12
CA2167184A1 (fr) 1995-10-12
ZA952769B (en) 1996-01-05
CN1095688C (zh) 2002-12-11
AU2231095A (en) 1995-10-23
CA2167184C (fr) 2002-02-26
EP0701478A1 (fr) 1996-03-20

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