CN1095688C - Densified carbon black adsorbent and method for adsorption of gas by using the adsorbent - Google Patents

Densified carbon black adsorbent and method for adsorption of gas by using the adsorbent Download PDF

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CN1095688C
CN1095688C CN95190498A CN95190498A CN1095688C CN 1095688 C CN1095688 C CN 1095688C CN 95190498 A CN95190498 A CN 95190498A CN 95190498 A CN95190498 A CN 95190498A CN 1095688 C CN1095688 C CN 1095688C
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carbon black
adsorbent
densified carbon
density
densified
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CN1128962A (en
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拉尔夫·U·伯斯
道格拉斯·M·史密斯
兰占·格索尔
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Cabot Corp
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    • 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
    • B01J20/20Solid 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

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  • Inorganic Chemistry (AREA)
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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 adsorption 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

Densified carbon black adsorbent and with the method for this adsorbents adsorb gas
The invention relates to a kind of adsorbent that comprises densified carbon black and with the method for this adsorbents adsorb gas.
The adsorption process of gas is the important component part in many commercial processes.The degree of absorption depends on the containing ability of this adsorbent to adsorbate.According to the purposes of adsorbent, the efficient of available several index evaluation adsorbents.The adsorbance of the adsorbance available units quality adsorbent of adsorbent or the adsorbance of unit volume adsorbent are represented.For some application, as absorption storage natural gas, because the space is restricted, so the adsorbance of unit volume adsorbent is to weigh the index of its efficient.Therefore, a kind of good adsorbent should have by unit mass with by all high adsorbance of unit volume.Because the bulk density of unit mass adsorbents adsorb amount and sorbing material has determined the adsorbance of unit volume adsorbent, so improve the adsorbance that the bulk density of adsorbent will increase the unit volume adsorbent.
Past is studied some carbon adsorbents.For example, people such as Mullhaupt are at " Carbon Adsorbents For Natural Gas Storage " (Internation-al Carbon Conference, 1992.6.21-26) disclose with active carbon in the literary composition and made the methane adsorbent, and the content of making the methane adsorbent with some carbon black.
US 4,999 330 (people such as Bose) has introduced with a kind of carbonaceous material of density and has made the methane adsorbent.Described according to this patent, under the situation of adsorbent density increase by 50% to 200%, the corresponding raising of unit volume adsorbents adsorb amount about 20% to about 100%.
Therefore, an object of the present invention is to provide a kind of densified carbon black, the adsorbance of the unit volume of this densified carbon black is higher than not densified carbon black unit volume adsorbance.
Another object of the present invention provides the method that the described densified carbon black of a kind of usefulness is made adsorbents adsorb gas.
The present invention realizes above-mentioned and other purpose by the novel sorbents that comprises densified carbon black is provided.After the density processing, described carbon black unit volume adsorbance ratio not densified carbon black preferably improves above 100% or higher, is up to 400% or higher.
The present invention's used " carbon black " speech can refer to any carbon black, as furnace black, and pyrolytic carbon black, dim, acetylene carbon black, or, be included in the carbon black that generates as accessory substance in the method that its primary product is not a carbon black with the carbon black that any other method is made.Described carbon black is that furnace black is relatively good.
The present invention provides a kind of method with densified carbon black adsorbents adsorb gas simultaneously.
Fig. 1 is that carbon black CB-1 and a kind of its nitrogen absorption BET surface area (SA) are 2050m 2The single shaft of/g active carbon is to the curve map of density process.
Fig. 2 be unit volume not densified carbon black, isobaric densified carbon black and single shaft to the curve map of densified carbon black to the methane adsorbance.
Process if carbon black is carried out density as described below, can obviously improve the unit bodies carbon deposit Black adsorbance. An important application of density adsorbent is for absorption storing natural gas, With unit volume of adsorbent under specified pressure and room temperature the Adsorption of methane amount is weighed this suction Attached dose usefulness. The adsorbance of unit volume adsorbent can be calculated by following formula:
                 V v=(V w)(d)
V in the formulawBe the adsorbance of sorbing material in the unit mass adsorbent, d is absorbent particles Density. After this sorbing material done density and process, density d had increased, so also just improve The adsorbance V of unit volumev
Can adopt in the known several densification technology of prior art any that carbon black is advanced The row density is processed. A kind of mode of compacting carbon black pellet is evenly to exert pressure from all directions (isobaric density). For example, can utilize pin type (pin) comminutor to make the carbon black particle densification. Pin type (pin) comminutor utilizes wetting fluid (normally water, but needn't be water) to produce Capillary force with the carbon black particle compacting and form particle. Typically, the water with metering is added to pin On the carbon black of the interior known quantity of formula (pin) comminutor, and stir this mixture. Syringe needle (pin) The capillary force of rolling action and wetting fluid forms particle.
During processing, the carbon black density can be used for carrying out the equipment bag of some other types of isobaric density Draw together (but being not limited to) cylinder comminutor and balling disk (-sc). The operation of this kind equipment is affiliated field, Especially the technical staff in the carbon black industry is known.
Another kind of carbon black density means are only from a direction exert pressure (single shaft is handled to density).This technology is common to every field, for example in catalysis and the pharmacy industry.This process can be utilized, and for example, following routine method realizes.Carefully the carbon black of known quality is packed in the former.In the concrete grammar described here, adopt the steel former of internal diameter 1.77cm (0.5 inch) circular cross-section.The formpiston that its external diameter is identical with the former internal diameter inserts former, assembly is placed between two pressing plates of a hydraulic press then.Exert pressure to formpiston, carbon black applies till the required pressure in to former.In this method, the 0.4mg carbon black is applied about 9080kg/cm 2(20,000 pounds of pressure) (is equivalent to be higher than 7000kg/cm in the former internal pressure of 1.77cm (0.5 inch) diameter 2(100,000psi) 3 hours.After the constant voltage phase finished, particle was taken out in decompression from former gradually.Can calculate particle volume from particle height and former diameter.Can calculate its density from particle weight and volume.
Table 1 is listed as several furnace blacks and the physical property thereof that the object of the invention is described and studies.The DBP of densified carbon black of the present invention is at least 150cc/100g.
Table 1: the character of some carbon blacks
Furnace black DBP iodine number CTAB BET
N 2S.A.
m 2/gBLACK?PEARLS R
2000
Carbon black 330 1,412 750 1500
CB-1 232 669 1021 1756
CB-2 340 655 1057 1936
CB-3 284 754 1081 1976
CB-4-1353-1896 carbon black analytical property
Measure carbon black to softex kw adsorptive value (CTAB) according to ASTM methods of test D 3765-85
Measure the iodine sorption value (I of carbon black according to ASTM methods of test D 1510 2No.)
Measure the nitrogen adsorption specific surface (N of carbon black according to ASTM methods of test D 3037-method A 2SA)
Measure carbon black to dibutyl phthalate adsorption value (DBP) according to ASTM methods of test D 3493-86
BLACK PEARLS R2000 furnace blacks are by Cabot Corporation produce and market, and its density was about 0.1-0.15g/cm before density was handled 3, handle back density with the isobaric density of pin type (pin) comminutor and increase to 0.27g/cm 3-0.3g/cm 3Single shaft after (as mentioned above) handled in density, BLACK PEARLS RThe density of 2000 carbon blacks is 0.45-0.6g/cm 3Similarly, label is the density of the another kind of furnace black of CB-1, before density is handled and single shaft after density is handled, density is from 0.1-0.15g/cm 3Bring up to 0.6-0.75g/cm 3
It is 2050m that Fig. 1 illustrates its nitrogen absorption BET surface area 2The single shaft of the active carbon powder of/gm (to call active carbon in the following text) and CB-1 carbon black is to the density conditional curve.Obviously, active carbon density increases not as carbon black CB-1.Although the initial density of carbon black is less than the initial density of active carbon, the final densities of carbon black CB-1 is greater than the final densities of active carbon when density one step-down circulation finishes.
Table 2 is listed two kinds of materials in the single shaft situation in each stage in the density experiment.Density is handled back active carbon density increase percentage and is about 96%, and the increase of carbon black CB-1 density is higher than 400%.Observe active carbon and do not keep any outward appearance that shape is arranged, and after breaking away from former, almost become powder at once, and carbon black CB-1 still keeps grain shape after leaving former.What deserves to be mentioned is that the density of the density specific activity charcoal of decompression back carbon black is much bigger.So can inference, the difference between active carbon and the carbon black structure makes carbon black show intrinsic superior density characteristic just.
Table 2: (numerical value is mutually to active carbon in the bracket to the density experimental data with carbon black CB-1 single shaft
The percentage that density material is not increased) density=0.3g/cm before the former that packs into of the stage active carbon carbon black materials in the density processing procedure 3Density=0.14g/cm 3Density=0.42g/cm in the preceding former of beginning is handled in density 3Density=0.25g/cm 3
Density=1.23g/cm is handled in the maximum density of material [40%] [79%] 3Density=1.33g/cm 35600kg/cm 2Density=0.59g/cm in former when [310%] [850%] (at 80000psi) density processing finishes 3Density=0.72g/cm 3Material [96%] [414%] leaves the material amorphism behind the former, is broken into the powder cylindrical particle
Example I and II list the example of several nonrestrictive gas absorption specifically.Example I and II have described the process of butane absorption under methane absorption under nitrogen absorption under 77 ° of K, 273 ° of K carbon dioxide absorption, the 298 ° of K and the 273 ° of K.These instantiations that carry out with gas with various under different temperatures and pressure condition have illustrated the general applicability of densified carbon black as adsorbent.EXAMPLE III is made adsorbent with several different densified carbon black, shows after any carbon black all can be handled through density as herein described to be used as adsorbent.It is therefore to be understood that the present invention never is subject to the following examples, these examples only are used to illustrate practicality of the present invention.
Example I-handle enhancing BLACK PEARLS by density RThe absorption property of 2000 carbon blacks
Table 3 is illustrated under different temperatures and the pressure condition, and gas with various measures by absorption is the BLACK PEARLS of benchmark with the unit volume RThe absorption property of 2000 carbon blacks.
Table 3: not density and density BLACK PEARLS R2000 carbon black unit volume adsorbents
Absorption property (numerical value is the percentage that relative not density adsorbent increases in the bracket) unit volume (cm 3) not density ((in density=0.12 (density=0.6 of isobaric density to the absorption property of the charcoal of density for loose pin type (pin) comminutor single shaft
G/cm 3) (density=0.29 g/cm 3)
G/cm 3) BET surface area 175.2 437[149%] 900[414%] m 2/ cm 3Charcoal micro pore volume 0.1158 0.2799[142%] 0.579[400%] cm 3/ cm 3298 ° of K of charcoal and 35 atmospheric pressure, 20 49[145%] 102[410%] following methane adsorbance cm 3Normal temperature-pressure (STP)/cm 3Charcoal
Can understand the ability of following densified carbon black adsorption of nitrogen, carbon dioxide and methane gas by above-mentioned table 3:
1) BET surface area: adsorption of nitrogen is a technology that is usually used in measuring carbon black surface area under 77 ° of K.Can carry out according to ASTM methods of test D 3037-method.One of ordinary skill in the art extensively utilize the BET surface area to judge practicality as the material of adsorbent for standard.The BET surface area is big more, and the absorption property to nitrogen under 77 ° of K of this adsorbent is good more.This surface area can be used m 2/ gm adsorbent or m 2/ cm 3Adsorbent is represented.As previously mentioned, the objective of the invention is to improve the surface area of unit volume adsorbent.Table 3 illustrates BLACK PEARLS R2000 carbon black density preceding and isobaric density or single shaft BET surface area data after density.The surface area that these data clearly demonstrate density processing back unit volume carbon black has increased.Therefore, this density processing method is extremely favourable to improving the carbon black absorption property, and the adsorbance that demonstrates nitrogen simultaneously increases.
2) adsorb the micro pore volume that obtains from carbon dioxide under 273 ° of K: the absorption of 273 ° of K carbon dioxides is to be used for characterizing the characterization of adsorption of gas near its critical-temperature the time.Adsorption theory is used for the carbon dioxide adsorpting data, also can calculates the micro pore volume of carbon black.In this case, utilize Dubinin and Astakhov method (referring to M.M.Dubinin, Progre-ss in Surface and Membrane Science Vol.9, people such as Cadenhead edit, Academic Press, New York (1975)) the mensuration micro pore volume.Table 3 illustrates equipressure or the single shaft micro pore volume to the forward and backward unit volume carbon black of density.By table 3 can know learn that the carbon black density is handled after, the micro pore volume of unit volume adsorbent has increased.This show carbon black carried out density and handles after, the amount of its unit volume absorbing carbon dioxide has improved, because CO 2Adsorbance be directly proportional with micro pore volume.
3) methane absorption under 298 ° of K: an important application in adsorbent future is to be automobile and other purposes storing natural gas with it.This practicality of adsorbent comes from the following fact: do not have the natural gas of the equivalent of depositing in the gas tank of adsorbent at an about 3000psi high pressure, can be stored in a pact (35-70) kg/cm 2In the gas tank that adsorbent is housed of suitable low-pressure (500-1000psi).In order to judge whether a kind of adsorbent is suitable for storing natural gas, under lab carry out the methane adsorption experiment usually.Because natural gas mainly is made up of methane, so the evaluation of available methane adsorbance is used for the performance of the adsorbent of storing natural gas.
The density of adsorbent is handled significant in the application aspect the natural gas to it, because will determine the practicality of this adsorbent by the amount of the available methane of adsorbent in the analytical unit volume basin.Adsorbent density is big more, and it is more little to load the required storage tank volume of a certain amount of absorbent particles.Therefore, if the amount of two kinds of its Unit Weight adsorbents adsorb methane of material identical (that is, it is more identical than absorption), then the adsorbance of its unit volume adsorbent of the material that density is bigger is bigger.
Fig. 2 illustrates BLACK PEARLS under following several situation RMethane adsorption isotherm under the 2000 carbon black room temperatures (in the unit volume adsorbent): density is 0.12g/cm 3Not densified carbon black, the density of isobaric density is 0.29g/cm in the pin type comminutor 3Carbon black and single shaft be 0.6g/cm to the density of density 3Carbon black.As shown in Figure 2, the adsorbance of unit volume densified carbon black is much higher than the not adsorbance of densified carbon black.So it is evident that, improve carbon black density, as mentioned above, directly cause increasing the adsorbance of unit volume adsorbent.
Adsorb butane on the CB-1 carbon black under the example II-273 ° K
The CB-1 carbon black adsorbs butane under 273 ° of K conditions of temperature, in order to confirm with densified carbon black absorption higher molecular gas, for example applicability of linear paraffin.The butane adsorbance is weighed the validity as the carbon black CB-1 of higher molecular adsorbent when being 549 holders with pressure.Table 4 has shown that carbon black CB-1 is before density and the change of single shaft unit volume adsorbents adsorb performance after density.Data in the table 4 clearly show that the unit volume adsorbent had increased the absorption property of butane after density was handled.
Table 4: (numeral shows carbon black CB-1 in the bracket to the absorption property of butane in the density front and back
With respect to the percentage increase of density material not) unit volume (cm 3) not density (" loose ") single shaft is to the absorption property (density=0.14g/cm of thickening carbon 3) (density=0.72g/cm 3) 549 holders, 0 ℃ of following CB-1 is to suction 34 184[441% of butane] attached performance cm 3Normal temperature-pressure (STP)/cm 3Charcoal
EXAMPLE III-variety classes not density and densified carbon black to the absorption property of gas:
EXAMPLE III has been studied the adsorption process on several different carbon blacks of several gases before and after handling through density, is applicable to the situation of using any densified carbon black to make adsorbent with explanation the present invention.
Table 5 is listed the BET surface area of several carbon blacks of measuring by nitrogen absorption under 77 ° of K.What this table was showed is the BET surface area that forward and backward unit volume is handled in density.All carbon blacks of listing table 5 in are after handling through density, and the BET surface area of unit volume carbon black all increases substantially.
Table 5: (bracket inner digital is relative to the BET surface area of various density and densified carbon black not
The percentage of the increase of density material not) black B ET surface area m 2/ cm 3BET surface area m 2/ cm 3
Charcoal, the charcoal of density not, single shaft is to the BLACK of density PEALS R175 900[414%] 2000 carbon black density=0.12g/cm 3Density=0.6g/cm 3CB-1 260 1289[396%]
Density=0.12g/cm 3Density=0.72g/cm 3CB-4 183 1037[467%]
Density=0.1g/cm 3Density=0.57g/cm 3
The listed data of table 6 demonstrate the adsorbance of the various carbon blacks of unit volume under 298 ° of K temperature and 35 atmospheric pressures to methane.These data representations be that to handle forward and backward be the adsorbance of benchmark with the unit volume in density.The unit volume adsorbance of every kind of densified carbon black shown in table 6 data is much higher than the not adsorbance of densified carbon black.
Table 6: density is handled the various carbon blacks of forward and backward unit volume the adsorbance of methane (is drawn together
Numeral is the relative percentage of the increase of densified carbon black not in number) carbon black not the methane of density material inhale single shaft to the density material
Attached amount cm 3STP/cm 3Charcoal methane adsorbance cm 3STP/cm 3Charcoal BLACK PEALS R20 102[410%] 2000 carbon black density=0.12g/cm 3Density=0.6g/cm 3CB-1 22 115[423%]
Density=0.14g/cm 3Density=0.72g/cm 3CB-2 20 102[410%]
Density=0.12g/cm 3Density=0.61g/cm 3CB-3 17 95[459%]
Density=0.1g/cm 3Density=0.55g/cm 3CB-4 18 105[483%]
Density=0.1g/cm 3Density=0.57g/cm 3
It is forward and backward that table 7 is listed the density processing, with the BLACK PEARLS of other unit representation R2000 carbon blacks are to the adsorbance of methane.As shown in table 7, carbon black process equipressure or single shaft are after density is handled, and the air storage amount obviously improves 142%-402%.
Table 7: influence (the BLACK PEARLS to the methane storage capacity is handled in density R2000 carbon blacks,
Under 4MPa and the 298 ° of K) adsorbent density is than adsorbance air storage amount
g/cm 3 g?CH 4/100g g?CH 4/1
The adsorbents adsorb agent not in 0.12 10.7 12.8 (loose frangible) pin type comminutor of density (142%) single shaft of 0.29 10.7 31 isobaric density to density to 0.6 10.7 64.2100,000pis (402%)
Above-mentioned example and respectively show listed data and be intended to specify the superiority of making adsorbent with densified carbon black.Although having, the adsorbance of its unit volume of the carbonaceous material density of prior art processing back is at most 100% increase, but densified carbon black of the present invention is compared with densified carbon black not, the unit volume adsorbent increases by 100% or more the adsorbance of gas or is higher, and can reach high as 400% or higher numerical value.These examples also show under different condition, and the absorption situation of gas with various on different carbon blacks shows that the present invention is applicable to utilize any carbon black to adsorb any gas.
When specifying preferred embodiment, can various improvement and replacement scheme be proposed not deviating from the present invention spirit and surmount under the situation of the scope of the invention.It is therefore to be understood that be here by way of example rather than the restriction mode the present invention is illustrated.

Claims (31)

1, a kind of adsorbent that comprises densified carbon black, than densified carbon black not, it has the increase of per unit volume at least 142% methane air storage amount under 298 ° of K, 35 atmospheric pressure.
2, by the described adsorbent of claim 1, wherein this densified carbon black is compared the not density increase 100%-500% of densified carbon black.
3, by the described adsorbent of claim 1, wherein the nitrogen adsorption specific surface of this densified carbon black is at least 600m 2/ g.
4, by the described adsorbent of claim 1, wherein the DBP of this densified carbon black is at least 150cc/100g.
5, by the described adsorbent of claim 1, wherein the bulk density of this densified carbon black is 0.3g/cm at least 3
6, by the described adsorbent of claim 1, wherein this densified carbon black is than densified carbon black not, its under 273 ° of K by CO 2Every cm of determining adsorption 3The micropore volume increase of charcoal is at least 142%.
7, by the described adsorbent of claim 1, wherein this densified carbon black is the furnace black of density.
8, by the described adsorbent of claim 1, wherein this adsorbent is an adsorbent
9, by the described adsorbent of claim 8, wherein this gas comprises methane, butane, nitrogen or carbon dioxide.
10, by the described adsorbent of claim 9, wherein this gas is methane.
11, by the described adsorbent of claim 1, wherein this densified carbon black is compared the not density increase 100%-500% of densified carbon black, nitrogen adsorption specific surface at least 600%, and DBP is at least 150cc/100g.
12, by the described adsorbent of claim 11, wherein this densified carbon black is than densified carbon black not, it has per unit volume charcoal at least 145% methane adsorbance under 298 ° of K, 35 atmospheric pressure increase.
13, a kind of usefulness contains the method for the adsorbents adsorb gas of densified carbon black, described method comprises with described adsorbent and contacts the sufficiently long time with described gas to be adsorbed to the described gas of small part, wherein said adsorbent is than densified carbon black not, and it has the increase of per unit volume at least 142% methane air storage amount under 298 ° of K, 35 atmospheric pressure.
14, by the described method of claim 13, wherein this densified carbon black compares the not density increase 100%-500% of densified carbon black.
15, by the described method of claim 13, wherein the nitrogen adsorption specific surface of this densified carbon black is at least 600m 2/ g.
16, by the described method of claim 13, wherein the DBP of this densified carbon black is at least 150cc/100g.
17, by the described method of claim 13, wherein the bulk density of this densified carbon black is 0.3g/cm at least 3
18, by the described method of claim 13, wherein this densified carbon black is than densified carbon black not, it has per unit volume charcoal at least 145% methane adsorbance under 298 ° of K, 35 atmospheric pressure increase.
19, by the described method of claim 13, wherein this densified carbon black comprises the furnace black of density.
20, by the described method of claim 13, wherein this gas comprises methane, butane, nitrogen or carbon dioxide.
21, by the described method of claim 20, wherein this gas is methane.
22, by the described method of claim 13, wherein this densified carbon black is compared the not density increase 100%-500% of densified carbon black, nitrogen adsorption specific surface at least 600%, and DBP is at least 150cc/100g.
23, the adsorbent of claim 1, wherein said densified carbon black is than densified carbon black not, and it has the increase of 142%-402% methane air storage amount.
24, by the described adsorbent of claim 1, wherein said adsorbent is than densified carbon black not, it has per unit volume charcoal at least 145% methane adsorbance under 298 ° of K, 35 atmospheric pressure increase.
25, by the described adsorbent of claim 24, wherein said adsorbent is than densified carbon black not, and it has the increase of 145%-483% methane adsorbance at least of per unit volume charcoal under 298 ° of K, 35 atmospheric pressure.
26, the method for claim 13, wherein said adsorbent is than densified carbon black not, and it has the increase of 142%-402% methane air storage amount.
27, a kind of adsorbent of forming by densified carbon black basically.
28, the adsorbent of claim 27, the density of wherein said densified carbon black is 0.29g/cm at least 3
29, the adsorbent of claim 27, the nitrogen adsorption specific surface of wherein said densified carbon black is at least 600m 2/ g.
30, the method for the adsorbents adsorb gas be made up of densified carbon black basically of a kind of usefulness, described method comprise with described adsorbent and contact the long enough time with described gas to be adsorbed to the described gas of small part.
31, the adsorbent of claim 30, the nitrogen adsorption specific surface of wherein said densified carbon black is at least 600m 2/ g.
CN95190498A 1994-04-05 1995-03-28 Densified carbon black adsorbent and method for adsorption of gas by using the adsorbent Expired - Fee Related CN1095688C (en)

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