CN105984864B - Carbon porous body, its manufacturing method and ammonia sorbing material - Google Patents
Carbon porous body, its manufacturing method and ammonia sorbing material Download PDFInfo
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Abstract
The present invention relates to a kind of carbon porous body, its manufacturing method and ammonia sorbing materials.In the carbon porous body, the volume by the hole of determining a diameter of below the 2nm of DFT analyses be 0.12mL/g hereinafter, and the Nitrogen adsorption isotherm at a temperature of 77K belong to the IV types of IUPAC classification (display porous body has the type of mesoporous).In the Nitrogen adsorption isotherm, in 0.5 relative pressure P/P0Under adsorbance be 0.8g/g hereinafter, and 0.9 relative pressure P/P0Under adsorbance be more than 1.5g/g.When changing air pressure in a specific range for specific gas, the carbon porous body can increase absorption or the desorption quantity of gas.The method of the manufacture carbon porous body of the present invention can be readily available such carbon porous body.When changing air pressure in a specific range for ammonia gas, ammonia sorbing material of the invention can increase absorption or the desorption quantity of ammonia gas.
Description
Technical field
The present invention relates to a kind of carbon porous body, its manufacturing method and ammonia sorbing materials.
Background technology
So far, carbon porous body has been used for various technical fields.Specifically, carbon porous body is utilized as electrochemistry electricity
The electrode material of container, the material of enzyme electrode, the sorbing material of canister and the purifying fuel equipment for loading biological fuel cell
Sorbing material.
Electrochemical capacitor is used due to the non-farad of wherein interionic transmission of the electronics not in electrode and electrolyte
The reaction or the faraday's reaction wherein transmitted between ion of the electronics in electrode and electrolyte and in electrode, (anode is negative
Pole) interface generate capacitance capacitor.Biological fuel cell includes cathode, just as in general fuel cell
Pole, electrolyte and diaphragm, and enzyme is used in cathode and anode.In such biological fuel cell, sugar is by negative side
Enzyme decompose and generate proton and electronics.Proton is transferred to just by electrolyte transport to side of the positive electrode, electronics by external circuit
Pole side.In anode so that carried out using the reduction reaction of proton and the oxygen of electronics by enzyme, as a result generate water.Pass through
These a series of reactions, can extract electric energy by biological fuel cell.Canister is be filled with carbon porous body canned
Canister, and be mounted in the car.In the engine stop of automobile, such canister is received and is adsorbed by pipeline
The gasoline vapour generated in fuel tank.On the other hand, when engine is run, fresh air is by canister, and thus filter is malicious
The gasoline vapour of tank release absorption and the fuel chambers that gasoline vapour is supplied to engine.In purifying fuel equipment, pass through
The impurity being included in fuel using the absorption of carbon porous body refines fuel.
Present inventors have developed a kind of carbon porous body, wherein being replaced with nitrogen-atoms to part carbon skeleton
(patent document 1).The carbon porous body has the microcellular structure that average pore size is below 2nm.Low-density with about 0.1 μm of aperture
Carbon foam is also known (patent document 2).The carbon foam by synthesizing as follows：To the polycondensation by resorcinol and formaldehyde and
The polymer cluster of acquisition carries out covalent cross-linking with synthesized gel rubber, gel is handled to manufacture airsetting at supercritical conditions
It glue and is carbonized to aeroge.
Reference listing
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-051828 bulletins
Patent document 2：U.S. Patent number 4873218
Invention content
Technical problem
So far, there is no the differences of the N2 adsorption amount with central hole structure and wherein in the relatively large range of relative pressure
Relative to the big known carbon porous body of relative pressure difference.Therefore, for the method for such carbon porous body to be easily manufactured
It is unknown.It is expected that such carbon porous body is not only used as the desorbing materials of specific gas, and it is used as electrochemical capacitor
Electrode material, the absorption for loading the material of enzyme electrode of biological fuel cell, the sorbing material of canister and purifying fuel equipment
Material.
In order to solve the problems, such as to have been completed the present invention above.The main object of the present invention is to provide a kind of with mesoporous
The structure and difference of N2 adsorption amount is more relative to the big carbon of relative pressure difference wherein in the relatively large range of relative pressure
Hole body.
Technical solution
Implement careful research as a result, the inventors found that by as follows as in order to realize object above
The carbon porous body of acquisition has good characteristic：In inert atmosphere at 550 DEG C~700 DEG C to the calcium salt of terephthalic acid (TPA) into
Row heating cleans compound by using acidic aqueous solution and removes calcium carbonate to form the compound of carbon and calcium carbonate.The hair
Now cause to complete the present invention.
Carbon porous body according to the present invention is analyzed the hole of determining a diameter of below 2nm by density functional theory (DFT)
Volume be 0.12mL/g hereinafter, and the Nitrogen adsorption isotherm at a temperature of 77K belong to International Union of Pure and Applied Chemistry
(IUPAC) the IV types of classification (display porous body has the type of mesoporous).In Nitrogen adsorption isotherm, in 0.5 relative pressure
P/P0Under adsorbance be 0.8g/g hereinafter, and 0.9 relative pressure P/P0Under adsorbance be more than 1.5g/g.
The method of the manufacture carbon porous body of the present invention includes：Terephthalic acid (TPA) in inert atmosphere at 550 DEG C~700 DEG C
Alkali salt heated compound to form carbon and alkaline earth metal carbonate, by using carbonate can be dissolved
Cleaning solution clean compound and by carbonate removal to obtain carbon porous body.
In addition, the ammonia sorbing material of the present invention is obtained by using the carbon porous body above the present invention.
Advantageous effect
Carbon porous body according to the present invention, when changing air pressure in a specific range for specific gas, Ke Yizeng
The absorption of aerating body or desorption quantity.In addition, the method for manufacture carbon porous body according to the present invention, can be readily available such
Carbon porous body.In addition, ammonia sorbing material according to the present invention, when changing air pressure in a specific range for ammonia gas,
Absorption or the desorption quantity of ammonia gas can be increased.
Description of the drawings
Fig. 1 is the figure of the adsorption isotherm of the IV types of IUPAC classification.
Fig. 2 is the figure of the Nitrogen adsorption isotherm of Examples 1 to 3 and comparative example 1,3 and 4.
Fig. 3 is the figure of the ammonia adsorption isotherm of Examples 1 to 3 and comparative example 1,3 and 4.
Fig. 4 is the figure for showing the relationship between the difference of N2 adsorption amount and the difference of ammonia adsorbance.
Fig. 5 is the figure of the Nitrogen adsorption isotherm of embodiment 2,3 and 6.
Specific embodiment
In the carbon porous body of the present invention, the hole of determining a diameter of below 2nm is analyzed by density functional theory (DFT)
Volume for below 0.12mL/g and preferably 0.11mL/g hereinafter, and the Nitrogen adsorption isotherm at a temperature of 77K belong to IUPAC point
The IV types of class.In Nitrogen adsorption isotherm, in 0.5 relative pressure P/P0Under adsorbance for 0.8g/g hereinafter, and 0.9
Relative pressure P/P0Under adsorbance be more than 1.5g/g.
For the carbon porous body of the present invention, the type by the Nitrogen adsorption isotherm of IUPAC class definitions is IV types (with reference to figure
1), display carbon porous body has mesoporous.In addition, the hole of a diameter of below 2nm is small, i.e. below 0.12mL/g.Therefore,
The carbon porous body of the present invention mainly has mesoporous composition.In addition, in the carbon porous body of the present invention, in Nitrogen adsorption isotherm, lead to
Cross from 0.9 relative pressure P/P0The N2 adsorption amount at place subtracts the relative pressure P/P 0.50The value that the N2 adsorption amount at place determines
For more than 0.7g/g.Therefore, in the relatively large range of relative pressure, the variable quantity of N2 adsorption amount is relative to relative pressure
Variable quantity is big.Therefore, when changing air pressure in a specific range for specific gas, body absorption or the solution of gas can be increased
Pipette.
The carbon porous body of the present invention can have such as 800m2The BET specific surface area of/more than g.Particularly, BET specific surfaces
Product is preferably 1000m2/ more than g, more preferable 1200m2/ more than g, and even more preferably from 1250m2/ more than g.This is because specific surface
Long-pending size is related to the improvement of various functional characteristics.Upper end value can be, for example, 2630m2/ below g.
The method of the manufacture carbon porous body of the present invention includes：Terephthalic acid (TPA) in inert atmosphere at 550 DEG C~700 DEG C
Alkali salt heated compound to form carbon and alkaline earth metal carbonate, by using washing for carbonate can be dissolved
It washs liquid and cleans compound by carbonate removal to obtain carbon porous body.This method is suitable for the above carbon porous body of the manufacture present invention.
In the method for the manufacture carbon porous body of the present invention, the example of phthalic acid includes phthalic acid (benzene -1,2- bis-
Formic acid), M-phthalic acid (benzene -1,3- dioctyl phthalate) and terephthalic acid (TPA) (benzene -1,4- dioctyl phthalate).Wherein, terephthalic acid (TPA) is
Preferably.The example of alkaline-earth metal includes magnesium, calcium, strontium and barium.Wherein, calcium is preferred.The alkali salt of phthalic acid can
To be obtained by buying commercial product.Alternatively, the alkali salt of phthalic acid can be by water by phthalic acid and alkali
The hydroxide of earth metal mixes to synthesize.In this case, the rubbing to the hydroxide of alkaline-earth metal for phthalic acid
That ratio only can use these compounds with the stoichiometry based on neutralization reaction formula.Alternatively, can use these compounds with
So that a kind of amount in compound is excessive relative to the amount of another compound.For example, molar ratio can be arranged on 1.5:1
~1:In the range of 1.5.It, can be by phthalic acid and alkali when the hydroxide of phthalic acid and alkaline-earth metal is mixed in water
The hydroxide of earth metal is heated to 50 DEG C~100 DEG C.
In the method for the manufacture carbon porous body of the present invention, the example of inert atmosphere includes nitrogen atmosphere and argon gas atmosphere.
Heating temperature is preferably arranged to 550 DEG C~700 DEG C.Heating temperature less than 550 DEG C is undesirable, because when under 77K
The relative pressure P/P of Nitrogen adsorption isotherm0When being 0.9, N2 adsorption amount is not big enough.Heating temperature higher than 700 DEG C is not preferred
, because cannot get carbon porous body.It is believed that the carbon and the compound of alkaline earth metal carbonate that obtain after the heating have wherein
Alkaline earth metal carbonate is located at the structure between the layer of stratiform carbide.Retention time at the heating temperature can be, for example, 50
Below hour.Particularly, the retention time is preferably 0.5~20 hour, and more preferable 1~10 hour.It is small for 0.5 when the retention time
When more than when, the compound for being sufficiently carried out carbon and alkaline earth metal carbonate is formed.When the retention time for 20 it is small when below when,
Obtain the carbon porous body with relatively large BET specific surface area.
In the method for the manufacture carbon porous body of the present invention, such as alkaline earth metal carbonate is the situation of calcium carbonate wherein
In, preferably by water or acidic aqueous solution as the cleaning solution that can dissolve alkaline earth metal carbonate.The example packet of acidic aqueous solution
Include the aqueous solution of hydrochloric acid, nitric acid, acetic acid, oxalic acid etc..It is thought that by implementing the cleaning, wherein alkaline-earth metal in the composite
Hole is partially changed into existing for carbonate.
The ammonia sorbing material of the present invention is formed by above-mentioned carbon porous body.In the ammonia sorbing material, by from 390kPa
Ammonia pressure under ammonia adsorbance to subtract the value that the ammonia adsorbance under the ammonia pressure of 300kPa determines be preferably 0.50g/g
More than.It this is because can be by the way that ammonia pressure be controlled to adsorb or discharge a large amount of ammonia.
Embodiment
[embodiment 1]
(synthesis of the calcium salt of terephthalic acid (TPA))
By terephthalic acid (TPA) (0.1mol) and calcium hydroxide (0.1mol) added in the water of 200mL, and at 80 DEG C
It is heated 4 hours in water-bath.The crystal of the calcium salt of obtained terephthalic acid (TPA) is detached, and wind at room temperature by filtering
It is dry.
(carbonization of the calcium salt of terephthalic acid (TPA))
The calcium salt (4g) of terephthalic acid (TPA) is arranged in electric tube furnace, and the inside of tube furnace is carried out with inert gas
It replaces (flow rate 0.1L/min).Nitrogen is used as inert gas.Alternatively, argon gas can be used.While gas stream is kept
Tube furnace is warming up to preset temperature in the period of one hour.In this embodiment, preset temperature is 550 DEG C.It is heating up
After the completion, while gas stream is kept, temperature under preset temperature is kept for 2 hours, is then cooled to room temperature.Knot
Fruit has manufactured the compound of carbon and calcium carbonate in tube furnace.
(the acid processing of compound)
Compound is taken out and is dispersed in the water of 500mL from tube furnace.Then, the hydrochloric acid of the 2mol/L of 50mL is added
In the dispersion liquid added to, and obtained mixture is stirred.It observes and foams due to the decomposition of calcium carbonate.To dividing
Dispersion liquid is filtered and is then dried.Aim carbon porous body (yield is obtained as a result,：About 1g).
[embodiment 2]
Carbon porous body is obtained as in the embodiment as in Example 1, and the difference lies in the carbonizations of the calcium salt in terephthalic acid (TPA)
In, the preset temperature of tubular type furnace temperature is 600 DEG C.
[embodiment 3]
Carbon porous body is obtained as in the embodiment as in Example 1, and the difference lies in the carbonizations of the calcium salt in terephthalic acid (TPA)
In, the preset temperature of tubular type furnace temperature is 700 DEG C.
[embodiment 4]
Carbon porous body is obtained as in the embodiment as in Example 1, and the difference lies in the calcium hydroxides relative to 0.1mol, make
With the terephthalic acid (TPA) of 0.15mol.
[embodiment 5]
Carbon porous body is obtained as in the embodiment as in Example 1, the difference lies in the terephthalic acid (TPA) relative to 0.1mol,
Use the calcium hydroxide of 0.15mol.
[embodiment 6]
Carbon porous body is obtained as in example 2, the difference lies in the carbonizations of the calcium salt in terephthalic acid (TPA)
In, the retention time under preset temperature (600 DEG C) is 20 hours.
[comparative example 1]
Carbon porous body is obtained as in the embodiment as in Example 1, and the difference lies in the carbonizations of the calcium salt in terephthalic acid (TPA)
In, the preset temperature of tubular type furnace temperature is 500 DEG C.
[comparative example 2]
The manufacture experiment of carbon porous body has been carried out as in the embodiment as in Example 1, and the difference lies in terephthalic acid (TPA)
In the carbonization of calcium salt, the preset temperature of tubular type furnace temperature is 800 DEG C.However, carbon porous body can not be obtained.
[comparative example 3]
The carbon porous body of comparative example 3 is commercially available activated carbon MESO-COAL (trade name) (by Cataler
Corporation is manufactured).
[comparative example 4]
The carbon porous body of comparative example 4 is commercially available activated carbon Bellfine BG-20-1 (trade name) (by AIR WATER
BELLPEARL INC. are manufactured).
[measurement of characteristic value]
For each carbon porous body of Examples 1 to 5 and comparative example 1,3 and 4, the characteristic value being shown in table 1 be by
What the measurement of the N2 adsorption under liquid nitrogen temperature (77K) was determined.Fig. 2 includes Examples 1 to 3 and comparative example 1,3 and 4 in 77K
Under Nitrogen adsorption isotherm.The Nitrogen adsorption isotherm figure of embodiment 4 and 5 and the Nitrogen adsorption isotherm figure of embodiment 1 are essentially identical,
Therefore the illustration of adsorption isotherm on the diagram is omitted.In table 1, BET specific surface area has been calculated by BET analyses.Pass through
Density functional theory (DFT) analysis has calculated the volume in the hole of a diameter of below 2nm.The shape in hole is rendered as the hole of slit-shaped
Structure.In 0.5 relative pressure P/P0The N2 adsorption amount A at placeN21 value and 0.9 relative pressure P/P0The N2 adsorption amount at place
AN22 value is read by Nitrogen adsorption isotherm figure.Difference between two values is defined as to the difference DELTA A of N2 adsorption amountN2(=
AN22-AN21)。
By table 1 it is readily apparent that in each carbon porous body of Examples 1 to 5, BET specific surface area is big, as
1200m2/ more than g, by small, as below the 0.12mL/g in the hole of determining a diameter of below the 2nm of DFT analyses.In addition,
The Nitrogen adsorption isotherm of the carbon porous body of Examples 1 to 3 shown in figure 2 belongs to the IV types (display by IUPAC class definitions
Porous body has the type of mesoporous, with reference to Fig. 1).It is shown substantially in the Nitrogen adsorption isotherm of embodiment 4 and 5 being not shown in figure
Identical result.Therefore, it is believed that the carbon porous body of Examples 1 to 5 mainly wants mesoporous to form.
In addition, for the carbon porous body of Examples 1 to 5, in Nitrogen adsorption isotherm, in 0.9 relative pressure P/P0Place
N2 adsorption amount AN22 be more than 1.5g/g, in 0.5 relative pressure P/P0The N2 adsorption amount A at placeN21 for 0.8g/g hereinafter, and nitrogen
The difference DELTA A of adsorbanceN2For more than 0.7g/g.These are the results show that carbon porous body for Examples 1 to 5, in relative pressure
In relatively large range, the variable quantity of N2 adsorption amount is big relative to the variable quantity of relative pressure.Therefore, for Examples 1 to 5
Carbon porous body, when changing air pressure in a specific range for specific gas (for example, nitrogen when), gas can be increased
Absorption or desorption quantity.
On the contrary, for the carbon porous body of comparative example 1, BET specific surface area is small, i.e., less than 1200m2/ g, in 0.9 opposite pressure
Power P/P0The N2 adsorption amount A at placeN22 is small as 1.02g/g, the difference DELTA A of N2 adsorption amountN2It is small as 0.34g/g.For than
Compared with the carbon porous body of example 3 and 4, the difference DELTA A of N2 adsorption amountN2It is minimum, as below 0.09g/g.Therefore, with Examples 1 to 5 not
Together, for comparative example 1,3 and 4, when changing air pressure in a specific range even for specific gas, gas can not be increased
Absorption or desorption quantity.
For each carbon porous body, use ammonia as specific gas and absorption measurement is carried out under 273K.Saturated vapor
It presses as 430kPa.It is inhaled by subtracting the ammonia under the ammonia pressure of 300kPa from the ammonia adsorbance under the ammonia pressure of 390kPa
Attached amount determines the difference DELTA A of ammonia adsorbanceNH3.Difference DELTA ANH3Value be shown in Table 1.Fig. 3 includes Examples 1 to 3 and comparative example
1st, 3 and 4 ammonia adsorption isotherm.The ammonia adsorption isotherm of embodiment 4 and 5 is essentially identical with embodiment 1, therefore is omitted
The illustration of adsorption isotherm on figure.Fig. 4 is the difference DELTA A for showing N2 adsorption amountN2With the difference DELTA A of ammonia adsorbanceNH3Between
The figure of relationship.Fig. 4 is shown in the difference DELTA A of N2 adsorption amountN2With the difference DELTA A of ammonia adsorbanceNH3Between there are good correlations
Property.
As shown in Table 1, it in the range of the ammonia pressure of 300kPa~390kPa, is obtained in Examples 1 to 5
The difference DELTA A of the big ammonia adsorbance of more than 0.50g/gNH3, and only obtain the 0.278g/g in comparative example 1 and comparing
The small value of below 0.06g/g in example 3 and 4.These are the results show that wherein using the situation of the carbon porous body of Examples 1 to 5
In, by controlling ammonia pressure that can adsorb and discharging a large amount of ammonia.
For the carbon porous body of embodiment 6, by the N2 adsorption under liquid nitrogen temperature (77K) as in Examples 1 to 5
Measurement characteristic value is determined.Fig. 5 shows the Nitrogen adsorption isotherm of embodiment 6.As a comparison, it also shows in Figure 5
The Nitrogen adsorption isotherm of embodiment 2 and 3.In embodiment 6, the volume in the hole of a diameter of below 2nm is 0.10mL/g, BET
Specific surface area is 1155m2/g.N2 adsorption amount AN21 is 0.61g/g, N2 adsorption amount AN22 be 1.52g/g, the difference DELTA of N2 adsorption amount
AN2For 0.91g/g.
By the above results it is readily apparent that in the carbon porous body of embodiment 6, BET specific surface area is less than 1200m2/ g,
This than Examples 1 to 5 BET specific surface area smaller, but in 800m2/ more than g, this is relatively large.It is determined by DFT analyses
Small, i.e., below the 0.12mL/g such as in Examples 1 to 5 in the hole of a diameter of below 2nm.In addition, such as embodiment 1~
The same in 5, the Nitrogen adsorption isotherm of the carbon porous body for the embodiment 6 being shown in FIG. 5 belongs to the IV types by IUPAC class definitions
(display porous body has the type of mesoporous, with reference to Fig. 1).Therefore, it is believed that the carbon porous body of embodiment 6 mainly wants mesoporous structure
Into.
In addition, for the carbon porous body of embodiment 6, in Nitrogen adsorption isotherm, in 0.9 relative pressure P/P0The nitrogen at place
Adsorbance AN22 be more than 1.5g/g, in 0.5 relative pressure P/P0The N2 adsorption amount A at placeN21 for 0.8g/g hereinafter, and N2 adsorption
The difference DELTA A of amountN2For more than 0.7g/g.These are the results show that carbon porous body for embodiment 6, in relative pressure relatively
In big range, the variable quantity of N2 adsorption amount is big relative to the variable quantity of relative pressure.Therefore, it is porous for the carbon of embodiment 6
Body, when changing air pressure in a specific range for specific gas (for example, nitrogen when), can increase gas absorption or
Desorption quantity.
In addition, the Nitrogen adsorption isotherm of embodiment 6 is similar with the Nitrogen adsorption isotherm of embodiment 2 and 3.As described above, such as
It is shown in Fig. 4, in the difference DELTA A of N2 adsorption amountN2With the difference DELTA A of ammonia adsorbanceNH3Between there are good correlations.Cause
This, it is believed that there is the carbon porous body of embodiment 6 ammonia similar with the ammonia characterization of adsorption of the carbon porous body of embodiment 2 and 3 to adsorb
Characteristic, and can adsorb and discharge a large amount of ammonia.
Industrial applicibility
The carbon porous body of the present invention is for example not only used as the sorbing material of nitrogen or ammonia, but also as electrochemistry
The electrode material of capacitor, the material of enzyme electrode for loading biological fuel cell, the sorbing material of canister, purifying fuel equipment
Sorbing material etc..
Claims (12)
1. a kind of carbon porous body, wherein be 0.12mL/g by the volume in the hole of determining a diameter of below the 2nm of DFT analyses hereinafter,
Nitrogen adsorption isotherm at a temperature of 77K belongs to the IV types of IUPAC classification, in the Nitrogen adsorption isotherm, in 0.5 phase
To pressure P/P0Under adsorbance be 0.8g/g hereinafter, and 0.9 relative pressure P/P0Under adsorbance be more than 1.5g/g.
2. carbon porous body according to claim 1, with 800m2The BET specific surface area of/more than g.
3. carbon porous body according to claim 2, with 1200m2The BET specific surface area of/more than g.
4. according to the carbon porous body of any one of claims 1 to 3, with 2630m2The BET specific surface area of/below g.
5. according to the carbon porous body of any one of claims 1 to 3, wherein the hole by determining a diameter of below the 2nm of DFT analyses
Volume be below 0.11mL/g.
6. a kind of method for manufacturing carbon porous body, including：
The alkali salt of phthalic acid heated in inert atmosphere at 550 DEG C~700 DEG C to form carbon and alkaline earth
The compound of metal carbonate and
By using the cleaning solution that can dissolve the carbonate clean the compound and by the carbonate removal, to obtain carbon
Porous body.
7. the method for manufacture carbon porous body according to claim 6, wherein by water by phthalic acid and alkaline-earth metal
Hydroxide mixes and obtains the alkali salt of the phthalic acid.
8. the method for manufacture carbon porous body according to claim 7, wherein hydrogen-oxygen of the phthalic acid to the alkaline-earth metal
The molar ratio of compound is 1.5:1~1:In the range of 1.5.
9. according to the method for the manufacture carbon porous body of any one of claim 6~8, wherein the alkaline-earth metal of the phthalic acid
Salt is the calcium salt of terephthalic acid (TPA).
10. according to the method for the manufacture carbon porous body of any one of claim 6~8, wherein the carbon porous body obtained is
The carbon porous body of claim 1.
11. a kind of ammonia sorbing material, it includes the carbon porous bodies of any one of claims 1 to 3.
12. ammonia sorbing material according to claim 11, wherein by subtracting from the ammonia adsorbance under the ammonia pressure of 390kPa
Go the ammonia adsorbance under the ammonia pressure of 300kPa and determining value is more than 0.50g/g.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3624004A (en) * | 1968-02-16 | 1971-11-30 | Standard Oil Co | Process for the production of active carbons |
| US4873218A (en) * | 1988-05-26 | 1989-10-10 | The United States Department Of Energy | Low density, resorcinol-formaldehyde aerogels |
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| JP2006016271A (en) * | 2004-07-02 | 2006-01-19 | National Institute Of Advanced Industrial & Technology | Porous carbon and its production method |
| JP2006016270A (en) * | 2004-07-02 | 2006-01-19 | National Institute Of Advanced Industrial & Technology | Basic metal compound-carrying carbon and its production method |
| JP5434389B2 (en) * | 2009-09-01 | 2014-03-05 | 株式会社豊田中央研究所 | Carbon porous body manufacturing method and power storage device |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3624004A (en) * | 1968-02-16 | 1971-11-30 | Standard Oil Co | Process for the production of active carbons |
| US4873218A (en) * | 1988-05-26 | 1989-10-10 | The United States Department Of Energy | Low density, resorcinol-formaldehyde aerogels |
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