JP2011012176A - Porous material, porous carbon material, adsorbent using the same and gas treatment device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a porous material which is excellent in heat resistance and adsorption-desorption continuous treatment ability and excellent in adsorption ability to substances having comparatively high polarity except water even in an environment exposed to the atmosphere containing moisture, to provide a porous carbon material obtained by subjecting the porous material to heat treatment, to provide an adsorbent using these and to provide a gas treatment device.SOLUTION: The porous material is used, having a three-dimensional porous structure formed by covalent bonds of an Si atom and one or more organic compounds selected from the group consisting of general formulae (1), (2) and (3).

Description

  The present invention uses a porous material that is not affected by the ability to adsorb relatively polar substances other than water even in an environment where moisture is present, or a porous carbon material obtained by heat-treating the porous material, and using them. The present invention relates to an adsorbent and a gas processing apparatus.

  Conventionally, it has been proposed to use zeolite as an adsorption / desorption material having excellent adsorption / desorption continuous processing capability (removal performance when adsorption and desorption are continuously repeated). However, in order to increase the amount of adsorption per volume of zeolite, even when zeolite is molded into an adsorbent, there is a limit to the improvement of the amount of adsorption.

On the other hand, in order to increase the amount of adsorption per volume, Non-Patent Document 1 proposes a coordination polymer metal complex comprising a metal and a coordination polymer and having a high specific surface area, and has attracted attention in recent years. However, the coordination polymer metal complex has a problem in that it adsorbs preferentially water, which is an atmospheric component, in an environment where it comes into contact with the atmosphere, and the adsorption ability for adsorbates other than water disappears. In addition, the coordination polymer metal complex has a problem that heat resistance in an environment exposed to the air is low, and it is difficult to perform a process of repeating adsorption and desorption continuously.

Non-Patent Document 2 proposes a hydrophobic porous material having a high specific surface area in order to solve the problems of adsorbability and heat resistance to adsorbates other than water in the environment exposed to the atmosphere as described above. Has been.
However, such an invention has improved the adsorbing ability and adsorbability to adsorbents other than water in an environment exposed to the atmosphere, but the adsorbing ability of a relatively polar substance such as isopropyl alcohol and methanol is not sufficient. There was a problem.

J. Am. Chem. Soc., 2004, 126, 15844-15851 Chem. Commun., 2008, 2462-2464

  The present invention was created in view of the current state of the prior art, and its purpose is to absorb adsorptive capacity, heat resistance, adsorption / desorption with respect to substances having relatively high polarity other than water even in an environment where moisture is present. An object of the present invention is to provide a porous material, a porous carbon material, an adsorbent using them, and a gas treatment device having excellent separation and continuous treatment capability.

As a result of intensive studies to solve the above problems, the present inventors have determined that the porous material as shown below can adsorb relatively highly polar substances other than water even in an environment where moisture is present. The porous carbon material is excellent in heat resistance and can be desorbed by heating. In addition to the above performance, it has been found that conductivity and durability can be improved, and the present invention has been completed.
1. A porous material having a three-dimensional porous structure formed by covalent bonding of Si atoms and one or more compounds selected from the group consisting of the following general formulas (1), (2) and (3).
(In the formula, n is an arbitrary number of 0 to 4, and R is the same or different, hydrogen atom, halogen atom, hydroxyl group, amino group, alkoxy group, nitro group, methoxymethyl group, carbon number of 1-20. Alkyl group, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, fluoroalkyl group having 1 to 20 carbon atoms, fluoroaryl group having 6 to 20 carbon atoms, fluoroaralkyl having 7 to 20 carbon atoms In R, groups adjacent to each other at the bonding position may be bonded to each other to form a ring, and X _a represents a nitrogen atom, a carbon atom, an oxygen atom or a sulfur atom, provided that n = in 4, R takes all hydrogen atoms, and, except when X _a is a carbon atom.)
(Wherein l and m each take an arbitrary number of 0 to 4, and R is the same or different, a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms. Represents an aryl group having 20 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroaryl group having 6 to 20 carbon atoms, and a fluoroaralkyl group having 7 to 20 carbon atoms. The groups adjacent to each other at the bonding position may be optionally bonded to form a ring, and X _b and X _c are the same or different and each represents a nitrogen atom, a carbon atom, an oxygen atom or a sulfur atom. The position of Xc is not limited as long as they are in the same aromatic ring, provided that l = 4 and m = 4, R is all hydrogen atoms, and _Xb and _Xc are carbon atoms. Except in cases.)
(Wherein, o and q are each an arbitrary number of 0 to 4, p is an integer of 0 to 6, and R is the same or different, hydrogen atom, halogen atom, hydroxyl group, amino group, sulfonic acid group, carbon number An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroaryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms In R, the groups adjacent to each other in R may be bonded to each other to form a ring, and X _{d to} X _k are the same or different and are a nitrogen atom, a carbon atom, Represents an oxygen atom or a sulfur atom.)
2. 1. The thermal decomposition temperature in an air atmosphere is 180 ° C. or higher. The porous material according to 1.
3. The adsorption ratio of 500 ppm of isopropyl alcohol at 30 ° C. and 20 RH% air atmosphere is 10 wt% or more. Or 2. The porous material according to 1.
4). 1-3. A porous carbon material obtained by heat-treating the porous material according to any one of 400 to 2000 ° C.
5. Said 1-4. An adsorbent comprising the porous material or the porous carbon material according to any one of the above.
6). Said 1-4. A gas processing apparatus using an adsorbent containing the porous material or the porous carbon material according to any one of the above.

  According to the present invention, the porous material is excellent in heat resistance and adsorption / desorption continuous processing ability, and excellent in the ability to adsorb relatively polar substances other than water even in an environment where moisture is present. It is possible to easily obtain a porous carbon material obtained by heat-treating a porous material, and an adsorbent and a gas processing apparatus using them.

The schematic diagram of the three-dimensional structure of the porous material of Example 1 is shown. The schematic diagram of a solvent vapor | steam adsorption performance test apparatus is shown. The schematic diagram of a gas processing apparatus is shown. The schematic diagram of a honeycomb is shown.

  First, the porous material of the present invention will be described.

  The porous material of the present invention is a tertiary formed by a covalent bond between an Si atom and one or more compounds selected from the group consisting of the following general formula (1), general formula (2), and general formula (3). It is a porous material having an original porous structure.

(In the formula, n is an arbitrary number of 0 to 4, and R is the same or different, hydrogen atom, halogen atom, hydroxyl group, amino group, alkoxy group, nitro group, methoxymethyl group, carbon number of 1-20. An alkyl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroaryl group having 6 to 20 carbon atoms, and a fluoroaralkyl group having 7 to 20 carbon atoms. In R, groups adjacent to each other at the bonding position may be bonded to each other to form a ring, and X _a represents a nitrogen atom, a carbon atom, an oxygen atom or a sulfur atom, where n = 4 in, R are all taking a hydrogen atom, and, except when X _a is a carbon atom.)

(Wherein l and m each take an arbitrary number of 0 to 4, and R is the same or different, a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms. Represents an aryl group having 20 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroaryl group having 6 to 20 carbon atoms, and a fluoroaralkyl group having 7 to 20 carbon atoms. The groups adjacent to each other at the bonding position may be optionally bonded to form a ring, and X _b and X _c are the same or different and each represents a nitrogen atom, a carbon atom, an oxygen atom or a sulfur atom. The position of Xc is not limited as long as they are in the same aromatic ring, provided that l = 4 and m = 4, R is all hydrogen atoms, and _Xb and _Xc are carbon atoms. Except in cases.)

(Wherein, o and q are each an arbitrary number of 0 to 4, p is an integer of 0 to 6, and R is the same or different, hydrogen atom, halogen atom, hydroxyl group, amino group, sulfonic acid group, carbon number An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroaryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms In R, the groups adjacent to each other in R may be bonded to each other to form a ring, and X _{d to} X _k are the same or different and are a nitrogen atom, a carbon atom, Represents an oxygen atom or a sulfur atom.)

Specifically, as the chemical structure represented by the general formula (1), for example, the following are preferable. These may be one kind or a combination of two or more.

Specifically, as the chemical structure represented by the general formula (2), for example, the following are preferable. These may be one kind or a combination of two or more.

Specifically, as the chemical structure represented by the general formula (3), for example, the following are preferable. These may be one kind or a combination of two or more.

A schematic diagram of the three-dimensional structure of the porous material of the present invention is shown in FIG. FIG. 1 is a schematic diagram showing a general formula (1), specifically, a state in which four anilines are bonded by a covalent bond around a Si atom to form a three-dimensional porous structure. The pore diameter of the porous material of the present invention is determined by the molecular structure size of the general formulas (1), (2) and (3), and is constant in the structure. The general formulas (1), (2) and (3) It is thought that gas is adsorbed in the micro space created by Si atoms.

For example, if general formula (1) is selected, a material having a smaller pore diameter can be obtained than when general formulas (2) and (3) are selected, and the specific surface area of the porous material can be increased. it can. As a result, the adsorption ability can be increased, and therefore, the general formula (1) is particularly preferable. In general formulas (1), (2), and (3), a nitrogen-containing compound is preferable from the viewpoint of improving the adsorptivity of polar substances. In addition, it is preferable that a functional group such as an amine or a sulfonic acid group is present in the molecule from the viewpoint of improving the adsorption ability of the polar substance.

A method for producing the porous material will be described.
The porous material of the present invention can be obtained as follows. That is, an organic compound in which both molecular ends of each of the general formula (1), the general formula (2), and the general formula (3) are substituted with a halogen atom and a Si compound are reacted in a solution in the presence of a catalyst, filtered, and dried. Can be obtained. In addition, the production | generation confirmation of the target object can be confirmed by infrared measurement etc., for example.
As the halogen atom in the organic compound in which both molecular ends are substituted with a halogen atom, Br is particularly preferable in order to obtain a porous material with high yield.
Examples of the Si compound used when the porous material of the present invention is synthesized include tetramethylsilane, trimethylsilylacetylene, vinyltrimethylsilane, trimethylsilylmethanol, trimethylsilylcyanide, tetraethyl orthosilicate, tetramethyl orthosilicate, and the like. .
As the catalyst used for the reaction, n-butyllithium is particularly preferable.
The solution used for the reaction is not particularly limited, but for example, tetrahydrofuran, hexane, dioxane, ether, methanol and the like are preferable, and it is preferable to use after dehydration.
The mixing ratio of each raw material is not particularly limited. For example, n is an organic compound in which both molecular ends of general formula (1), general formula (2), and general formula (3) are substituted with halogen atoms. It is preferable that 1.5 to 3 times mol of butyl lithium, 0.1 to 1 times mol of the Si compound, and 30 to 100 parts by mass of the solution. Even if the mixing ratio is other than the above, a porous material can be obtained, but the yield and adsorption ability may be reduced.
Although reaction temperature in particular is not restrict | limited, -78-10 degreeC is preferable, More preferably, it is -68-0 degreeC, More preferably, it is -60--10 degreeC. If the reaction temperature is less than −78 ° C., the reaction time tends to be longer, and if it exceeds 10 ° C., the yield of the porous material may be lowered or the adsorption ability may be lowered.
The reaction time is preferably 1 minute to 96 hours, more preferably 5 minutes to 72 hours, and even more preferably 10 minutes to 48 hours. If the reaction time is less than 1 minute, the yield of the porous material tends to be low, and if it exceeds 96 hours, the porous material may be decomposed.
The reaction is preferably performed in an inert atmosphere, and is preferably performed in at least one atmosphere selected from the group consisting of helium, neon, krypton, xenon, argon, nitrogen, ammonia, and acetonitrile. If the reaction is carried out in an active atmosphere, the yield of the porous material may be lowered. The drying of the porous material after the reaction is not particularly limited, but must be performed at a temperature lower than the thermal decomposition temperature of the porous material, for example, preferably 100 to 180 ° C, more preferably under 110 to 150 ° C, It is preferable to heat-dry under vacuum for 30 to 180 minutes.

The organic compound in which both ends are substituted with Br used for synthesizing the porous material of the present invention will be described. Specific examples of the organic compound in which both molecular ends of the general formula (1) and the general formula (2) are substituted with Br are represented by chemical formulas (4), (5), (6), and (7). Examples are those in which both ends of the molecular structure of the organic compound are substituted with Br. For example, 1,4-dibromotetrafluorobenzene, 1,4-dibromo-2-methoxy-3-nitrobenzene, 1,4-dibromo-2,5-bis-methoxymethylbenzene, 9,10-dibromo-2-methyl Anthracene, 1,4-dibromo-2,3,5,6-tetramethoxybenzene, 2,5-dibromonitrobenzene, 4,7-dibromobenzo [c] [1,2,5] thiadiazole, 2,5- Dibromobenzotrifluoride, 2,5-dibromoaniline, 1,4-dibromo-2-fluorobenzene, 2,5-dibromohydroquinone, 2,5-dibromopyridine, 2,5-dibromo-3-methylpyridine, 3, 6-dibromo-2-methylpyridine, 1,4-dibromo-2,5-dimethoxybenzene, 1,4-dibromo-2,5-diflu Robenzen, 4,4'-dibromo-2-biphenyl amine, can be preferably used 4,4'-dibromo-octafluorobiphenyl 4,4'-dibromo-3-phenylpyridine and the like. These can use a commercial item.

Specifically, as an organic compound in which both molecular ends of the general formula (3) are substituted with Br, both ends of the molecular structure of the organic compound represented by the chemical formulas (8) and (9) are substituted with Br. Are illustrated.
Although a commercial item can also be used, it can obtain as follows. For example, in an inert atmosphere such as helium, neon, krypton, xenon, argon, nitrogen, ammonia, acetonitrile, add aromatic diamine derivative and bromobenzoic acid derivative to 116% polyphosphoric acid at 80-150 ° C., After stirring for 1 to 35 hours, the reaction solution can be obtained by reprecipitation in water, filtration and drying. When the reaction temperature is less than 80 ° C., the reaction time tends to be long, and when it exceeds 150 ° C., there is a possibility that the organic compound having both molecular ends substituted with Br may be thermally decomposed. If the reaction time is less than 1 hour, the proportion of unreacted substances tends to be high and the yield tends to be low. If the reaction time exceeds 35 hours, the organic compound having both ends of the molecule substituted with Br may be decomposed.
As for the mixing ratio of each raw material, for example, it is preferable to mix the bromobenzoic acid derivative at a ratio of 1.5 to 3 times mol and 116% polyphosphoric acid at a ratio of 10 to 100 parts by mass with respect to the aromatic diamine derivative. Other than the mixing ratio, an organic compound in which both molecular ends of the general formula (3) are substituted with Br can be obtained, but the yield may be lowered or the cost may be increased.
The aromatic diamine derivative is a compound in which the ortho position with respect to the amide group of the aromatic diamine is substituted with —OH group, —NH ₂ group, or —SH group, and is represented by the following formula (10), for example. Compounds can be used. These can use a commercial item.

As the bromobenzoic acid derivative, for example, a compound represented by the following formula (11) can be used. These can use a commercial item.

Next, the porous carbon material of the present invention will be described.
The porous carbon material of the present invention can be obtained by heat-treating the aforementioned porous material. For example, in at least one atmosphere selected from the group consisting of helium, neon, krypton, xenon, argon, nitrogen and ammonia, preferably 400 to 2000 ° C, more preferably 500 to 1700 ° C, and still more preferably 600 to 1500 ° C. Heat treatment with The heat treatment time is preferably 30 minutes to 4 hours, more preferably 1 to 3 hours, and even more preferably 1 to 2 hours. By performing the heat treatment, the porous material is carbonized, and the conductivity and durability are improved. When the heat treatment temperature is lower than 400 ° C. or shorter than 30 minutes, the improvement in conductivity and durability is insufficient, and when it is higher than 2000 ° C. or longer than 4 hours, the adsorptive capacity decreases. Can happen. Heat treatment can also be performed by irradiating the porous material with microwaves. There is no particular limitation on microwave irradiation, but it is preferably performed under at least one atmosphere selected from the group consisting of helium, neon, krypton, xenon, argon, nitrogen, and ammonia, or under reduced pressure. The wavelength of the microwave used is preferably in the range of 0.1 to 100 cm, and the frequency is preferably in the range of 300 MHz to 30 GHz. When the wavelength is greater than 100 cm or when the frequency is less than 300 MHz, carbonization tends to be insufficient, and when the wavelength is less than 0.1 cm or greater than 30 GHz, the adsorptive capacity may be lowered.

In addition, the porous carbon material of the present invention can be increased in specific surface area by removing the metal by acid treatment or base treatment after heat treatment. The acid is not particularly limited, but is at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and hydrogen peroxide, and the base is not particularly limited, but sodium hydroxide, potassium hydroxide, hydroxide It is at least one base selected from the group consisting of ammonium and hydroxylamine. In the treatment method, for example, the metal can be removed by immersing the porous carbon material in the acid aqueous solution or the base aqueous solution for 1 to 72 hours.

Since the porous material or porous carbon material of the present invention is a porous body having a pore structure inside, it can be used as an adsorbent. Since the porous material or porous carbon material of the present invention has a fixed pore size at the molecular level and is constant in structure, there is little problem that the adsorbed gas is difficult to desorb and the adsorption / desorption continuous processing capability is improved. Excellent.
The porous material material of the present invention or the porous carbon material can adsorb gas, for example, by bringing it into contact with a gas to be adsorbed. Further, the adsorbed gas may be desorbed by performing a gas adsorption process on the porous material under a pressurized condition, and heating and / or depressurizing the gas.
The porous material material and the porous carbon material preferably have a thermal decomposition temperature of 180 ° C. or higher in an air atmosphere. When desorbing the gas adsorbed on the porous material, for example, by heating at 180 ° C. or higher in an air atmosphere, the adsorbed gas can be desorbed, and the process of continuously repeating adsorption and desorption is performed. Is possible. If the thermal decomposition temperature in an air atmosphere is less than 180 ° C., it is not preferable because when the gas is desorbed, the porous material may be thermally decomposed and the adsorption capacity may be lowered.
Here, the thermal decomposition temperature is 180 ° C. or more. Specifically, for example, the thermal decomposition temperature is analyzed at a rate of temperature increase of 10 ° C./min under a stream of air using a commercially available thermogravimetric analyzer. The temperature at the time when the sample weight at 5% decreases by 180% is said.

The substance to be adsorbed may be a substance having a relatively high polarity or a substance having a relatively low polarity. Examples of the substance include carbonyl compounds such as aldehydes, ketones, and esters, olefins, alcohol compounds, and the like. Examples of the substances described below include hexane, cyclohexane, toluene, 1-butanol, 1-hexanol, xylene, paradichlorobenzene, and tetrahydrofuran. Aniline, chlorobenzene, acetic acid, diethyl ether, 1-4 dioxane, freon, propylene, benzene, methylamine, anisole, nitrobenzene and the like.

The porous material and the porous carbon material of the present invention are characterized in that they are excellent in adsorbing ability with respect to substances having relatively high polarity. The adsorption rate of isopropyl alcohol 500 ppm in an air atmosphere at 30 ° C. and 20 RH% is preferably 10 wt% or more, more preferably 15 wt% or more, and further preferably 20 wt% or more. The higher the isopropyl alcohol adsorption rate of a porous material in an air atmosphere at 30 ° C. and 20 RH%, the better, and when it is less than 10 wt%, the performance as an adsorbent is low, and the use of the porous material when adsorbing and removing gas is used. You have to increase the amount.
Here, the adsorption rate q of isopropyl alcohol can be measured according to JIS-K1474, and can be evaluated as follows, for example. Solvent vapor adsorption performance test apparatus having a constant temperature bath or a constant temperature water bath N adjusted to 30 ° C. ± 0.5 ° C. by placing 0.5 g of a porous material or a porous carbon material in an adsorption test U-shaped tube D (see FIG. 2), a mixed air of 500 ppm of isopropyl alcohol is allowed to flow in a 20 RH% air atmosphere and adsorbed for 60 minutes, and the weight increase of the porous material or the porous carbon material can be measured. That is, the adsorption rate q can be calculated from the following equation (1).

[Equation 1]
q (%) = P / S × 100 (1)
P: Increase in porous material or porous carbon material (g)
S: Mass of porous material or porous carbon material (g)

The adsorbent may use the porous material or the porous carbon material as a powder, or may be processed into a pellet or granule using a binder or a carrier if necessary, and may be an extrusion method in some cases. It is also possible to use it after being formed into a honeycomb shape.

Next, the gas processing apparatus of the present invention will be described. The gas treatment apparatus of the present invention is not particularly limited, but a material filled or molded with the porous material or the porous carbon material is disposed in a part C on the line as shown in the schematic diagram of FIG. Can be used.

The gas treatment apparatus of the present invention is not particularly limited to that shown in FIG. 3, but a porous material or a porous carbon material filled or molded on the line as shown in the schematic diagram of FIG. 3. In the adsorption process, the valve A is opened and the valve B is closed, and the substance to be adsorbed is vented and removed by adsorption. On the other hand, in the desorption process, the valve B is opened and the valve A is opened. It is preferable to remove the adsorbate by continuously repeating the operation of closing, venting a small amount of heated air, and desorbing the adsorbed substance. Further, the desorbed substance may be subjected to oxidative decomposition treatment by a combustion device, for example.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the Examples, the thermal decomposition temperature, the isopropyl alcohol adsorption rate, and the isopropyl alcohol removal rate were evaluated as follows.

[Measurement of adsorption performance (measurement of isopropyl alcohol adsorption rate q): (according to JIS-K1474)]
Solvent vapor adsorption performance test apparatus having a constant temperature bath or a constant temperature water bath N adjusted to 30 ° C. ± 0.5 ° C. by placing 0.5 g of a porous material or a porous carbon material in an adsorption test U-shaped tube D (see FIG. 2), a mixed air of isopropyl alcohol of 500 RH and 20 RH% was flowed and adsorbed for 60 minutes, and the weight increase of the porous material or the porous carbon material was measured. The adsorption rate q was calculated from the following formula (1).

[Equation 1]
q (%) = P / S × 100 (1)
P: Increase in porous material or porous carbon material (g)
S: Mass of porous material or porous carbon material (g)

[Evaluation of thermal decomposition temperature]
The thermal decomposition temperature was analyzed with a commercially available thermogravimetric analyzer (TA Instruments, TGA2950) under an air stream at a rate of temperature increase of 10 ° C / min, and the 5 wt% pyrolysis temperature in an air atmosphere was 180 ° C. It was evaluated whether it was above. In the table, ◯ indicates that the 5% by weight pyrolysis temperature in an air atmosphere is 180 ° C. or more, and X indicates that the 5% by weight pyrolysis temperature in an air atmosphere is less than 180 ° C.

[Evaluation of continuous adsorption / desorption treatment: measurement of isopropyl alcohol removal rate (η)]
The isopropyl alcohol removal rate (η) was measured using a gas treatment device (FIG. 3). The removal rate was calculated from the following formula (2). In addition, the adsorption element C used for the measurement has a honeycomb with a wavelength (P) of 3.1 mm and a wave height (H) of 2.1 mm, in which a porous material or a porous carbon material is contained at a content of 70 wt% (see FIG. 4) was laminated so as to be 25 cm × 25 cm × 45 cm.

The adsorption / desorption operation is performed by switching between the valve A and the valve B. In the adsorption operation, the valve A is opened (valve B is closed), and the process gas isopropyl alcohol is introduced into the adsorption element C for a certain period of time. The isopropyl alcohol in the processing gas is removed by adsorption. In the desorption operation, the valve B is opened (valve A is closed), and heated air is introduced into the adsorption element C for a certain period of time, and the adsorbed isopropyl alcohol is desorbed to regenerate the adsorption element. This adsorption operation and desorption operation are continuously performed to treat isopropyl alcohol. The measurement of the processing gas concentration and the processing gas outlet concentration is performed every 1 hour from the start of operation of the apparatus, and the adsorption and desorption operations are sufficiently repeated so that the isopropyl alcohol outlet concentration shows a constant concentration and does not change. Went until it stabilized.

The processing gas conditions and the operating conditions of the equipment are
Processing gas Isopropyl alcohol processing gas concentration 300 (ppm)
Adsorption wind speed 1.5 (m / s)
Adsorption air volume / Desorption air volume 7 (-)
Desorption temperature 180 (℃)
Adsorption time 9 to 54 (min)
Desorption time 1-6 (min)

[Equation 2]
η (%) = (I−O) / I × 100 (2)
I: Process gas concentration (ppm)
O: Process gas outlet concentration (ppm)

Example 1
After adding 300 mL of tetrahydrofuran to 3.8 g of 2,5-dibromoaniline under an argon atmosphere and stirring at -10 ° C for 10 minutes, 18.8 mL of n-butyllithium was added dropwise. Then, after stirring for 30 minutes at -10 degreeC, 1.6 g of tetraethyl orthosilicates were dripped, and after stirring for 15 minutes at -10 degreeC, cooling was stopped and it stirred until it became room temperature. The reaction solution was poured into 3 L of water, and the powder was taken out by suction filtration. The powder was sufficiently washed with water, tetrahydrofuran and ethanol, and then vacuum dried at 110 ° C. to obtain a porous material.
It was evaluated whether the 5 wt% pyrolysis temperature of the porous material in an air atmosphere was 180 ° C or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said porous material was implemented. The results are shown in Table 1.
Next, the porous material is applied to the gas treatment apparatus (FIG. 3) and is put into a part C on the line. In the adsorption operation, 300 ppm of isopropyl alcohol is passed through 40 ° C. and 60 RH% gas, and isopropyl alcohol is added. On the other hand, in the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C. with 1/7 of the air volume is vented to the air volume of the adsorption operation, and the operation of desorbing isopropyl alcohol is continuously performed. The isopropyl alcohol removal rate was measured.

(Example 2)
The porous material obtained in Example 1 was heated to 600 ° C. at 5 ° C./min in a nitrogen atmosphere and heat-treated at 600 ° C. for 1 hour. Thereafter, it was allowed to cool to room temperature to obtain a porous carbon material.
It was evaluated whether the 5 wt% pyrolysis temperature of the porous carbon material in an air atmosphere was 180 ° C or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said porous carbon material was implemented. The results are shown in Table 1.
Next, the porous carbon material is adapted to a gas processing apparatus (FIG. 3), put into a part C on the line, and in the adsorption operation, isopropyl alcohol 300 ppm of 40 ° C., 60 RH% gas is vented to isopropyl alcohol. In the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C., which is 1/7 of the air volume, is continuously vented to desorb isopropyl alcohol. The isopropyl alcohol removal rate was measured.

(Example 3)
After adding 300 mL of ether to 4.9 g of 4,4-dibromo-2-biphenylamine under a nitrogen atmosphere and stirring at −60 ° C. for 10 minutes, 18.8 mL of n-butyllithium was added dropwise. Then, after stirring for 30 minutes at -60 degreeC, 1.6 g of tetraethyl orthosilicate was dripped, and after stirring for 60 minutes at -60 degreeC, it cooled and stopped until it became room temperature. The reaction solution was poured into 3 L of water, and the powder was taken out by suction filtration. The powder was thoroughly washed with water, ether, and ethanol, and then vacuum dried at 110 ° C. to obtain a porous material.
It was evaluated whether the 5 wt% pyrolysis temperature of the porous material in an air atmosphere was 180 ° C or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said porous material was implemented. The results are shown in Table 1.
Next, the porous material is applied to the gas treatment apparatus (FIG. 3) and is put into a part C on the line. In the adsorption operation, 300 ppm of isopropyl alcohol is passed through 40 ° C. and 60 RH% gas, and isopropyl alcohol is added. On the other hand, in the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C. with 1/7 of the air volume is vented to the air volume of the adsorption operation, and the operation of desorbing isopropyl alcohol is continuously performed. The isopropyl alcohol removal rate was measured.

Example 4
The porous material obtained in Example 3 was heated to 800 ° C. at 5 ° C./min in a nitrogen atmosphere and heat-treated at 800 ° C. for 2 hours. Thereafter, it was allowed to cool to room temperature to obtain a porous carbon material.
It was evaluated whether the 5 wt% pyrolysis temperature of the porous carbon material in an air atmosphere was 180 ° C or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said porous carbon material was implemented. The results are shown in Table 1.
Next, the porous carbon material is adapted to a gas processing apparatus (FIG. 3), put into a part C on the line, and in the adsorption operation, isopropyl alcohol 300 ppm of 40 ° C., 60 RH% gas is vented to isopropyl alcohol. In the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C., which is 1/7 of the air volume, is continuously vented to desorb isopropyl alcohol. The isopropyl alcohol removal rate was measured.

(Example 5)
The porous carbon material obtained in Example 4 was stirred in a 3M aqueous hydrochloric acid solution at 60 ° C. for 24 hours, and the powder was taken out by suction filtration. The powder was thoroughly washed with water and then vacuum-dried at 110 ° C.
It was evaluated whether the 5 wt% pyrolysis temperature of the porous carbon material in an air atmosphere was 180 ° C or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said porous carbon material was implemented. The results are shown in Table 1.
Next, the porous carbon material is adapted to a gas processing apparatus (FIG. 3), put into a part C on the line, and in the adsorption operation, isopropyl alcohol 300 ppm of 40 ° C., 60 RH% gas is vented to isopropyl alcohol. In the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C., which is 1/7 of the air volume, is continuously vented to desorb isopropyl alcohol. The isopropyl alcohol removal rate was measured.

(Example 6)
In a nitrogen atmosphere, 8.5 g of 1,2,4,5-tetraaminobenzene tetrahydrochloride and 12.3 g of 5-bromo-2-pyridinebenzoic acid were added to 59.3 g of 116% polyphosphoric acid, and at 120 ° C., After stirring for 21 hours, the reaction solution was reprecipitated into 1 L of water, and the precipitated powder was taken out from the suction filtration. The obtained powder was sufficiently washed with water and then vacuum dried at 90 ° C. to obtain a dibromobisbenzimidazole derivative.
Methanol (500 mL) was added to 7.0 g of the dibromobisbenzimidazole derivative under a nitrogen atmosphere and stirred at −10 ° C. for 10 minutes, and then 18.8 mL of n-butyllithium was added dropwise. Then, after stirring at −10 ° C. for 2 hours, 1.6 g of tetraethyl orthosilicate was added dropwise, stirred at −10 ° C. for 12 hours, and then cooled down to room temperature. The reaction solution was poured into 5 L of water, and the powder was taken out by suction filtration. The powder was thoroughly washed with water and methanol and then vacuum dried at 110 ° C. to obtain a porous material.
It was evaluated whether the 5 wt% pyrolysis temperature of the porous material in an air atmosphere was 180 ° C or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said porous material was implemented. The results are shown in Table 1.
Next, the porous material is applied to the gas treatment apparatus (FIG. 3) and is put into a part C on the line. In the adsorption operation, 300 ppm of isopropyl alcohol is passed through 40 ° C. and 60 RH% gas, and isopropyl alcohol is added. On the other hand, in the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C. with 1/7 of the air volume is vented to the air volume of the adsorption operation, and the operation of desorbing isopropyl alcohol is continuously performed. The isopropyl alcohol removal rate was measured.

(Example 7)
7.4 g of 2,5-diamino-1,4-benzenedithiol dihydrochloride and 12.3 g of 4-bromobenzoic acid were added to 59.3 g of 116% polyphosphoric acid under a nitrogen atmosphere, and the mixture was stirred at 80 ° C. for 35 hours. Then, the reaction solution was reprecipitated in 1 L of water, and the precipitated powder was taken out from the suction filtration. The obtained powder was sufficiently washed with water and then vacuum-dried at 90 ° C. to obtain a dibromobisbenzothiazole derivative.
To 7.5 g of the dibromobisbenzothiazole derivative, 500 mL of 1,4-dioxane was added under an argon atmosphere and stirred at −10 ° C. for 10 minutes, and then 18.8 mL of n-butyllithium was added dropwise. Then, after stirring at −10 ° C. for 5 hours, 1.6 g of tetraethyl orthosilicate was added dropwise, stirred at −10 ° C. for 24 hours, and then cooled down to room temperature. The reaction solution was poured into 5 L of water, and the powder was taken out by suction filtration. The powder was sufficiently washed with water and 1,4-dioxane, and then vacuum dried at 110 ° C. to obtain a porous material.
It was evaluated whether the 5 wt% pyrolysis temperature of the porous material in an air atmosphere was 180 ° C or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said porous material was implemented. The results are shown in Table 1.
Next, the porous material is applied to the gas treatment apparatus (FIG. 3) and is put into a part C on the line. In the adsorption operation, 300 ppm of isopropyl alcohol is passed through 40 ° C. and 60 RH% gas, and isopropyl alcohol is added. On the other hand, in the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C. with 1/7 of the air volume is vented to the air volume of the adsorption operation, and the operation of desorbing isopropyl alcohol is continuously performed. The isopropyl alcohol removal rate was measured.

(Example 8)
6.4 g of 4,6-diaminoresorcinol dihydrochloride and 12.1 g of 6-bromonicotinic acid were added to 59.3 g of 116% polyphosphoric acid under a nitrogen atmosphere, and the mixture was stirred at 150 ° C. for 1 hour. Was reprecipitated in 1 L of water, and the precipitated powder was taken out by suction filtration. The obtained powder was sufficiently washed with water and then vacuum dried at 90 ° C. to obtain a dibromobisbenzoxazole derivative.
To 7.5 g of the dibromobisbenzoxazole derivative, 500 mL of 1,4-dioxane was added under an argon atmosphere and stirred at −10 ° C. for 10 minutes, and then 18.8 mL of n-butyllithium was added dropwise. Then, after stirring at −10 ° C. for 12 hours, 1.6 g of tetraethyl orthosilicate was added dropwise, stirred at −10 ° C. for 24 hours, and then cooled until the temperature reached room temperature. The reaction solution was poured into 5 L of water, and the powder was taken out by suction filtration. The powder was sufficiently washed with water and 1,4-dioxane, and then vacuum dried at 110 ° C. to obtain a porous material.
It was evaluated whether the 5 wt% pyrolysis temperature of the porous material in an air atmosphere was 180 ° C or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said porous material was implemented. The results are shown in Table 1.
Next, the porous material is applied to the gas treatment apparatus (FIG. 3) and is put into a part C on the line. In the adsorption operation, 300 ppm of isopropyl alcohol is passed through 40 ° C. and 60 RH% gas, and isopropyl alcohol is added. On the other hand, in the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C. with 1/7 of the air volume is vented to the air volume of the adsorption operation, and the operation of desorbing isopropyl alcohol is continuously performed. The isopropyl alcohol removal rate was measured.

Example 9
The porous material obtained in Example 8 was heated to 1500 ° C. at 5 ° C./min in an argon atmosphere and heat-treated at 1500 ° C. for 1 hour. Thereafter, it was allowed to cool to room temperature to obtain a porous carbon material.
It was evaluated whether the 5 wt% pyrolysis temperature of the porous carbon material in an air atmosphere was 180 ° C or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said porous carbon material was implemented. The results are shown in Table 1.
Next, the porous carbon material is adapted to a gas processing apparatus (FIG. 3), put into a part C on the line, and in the adsorption operation, isopropyl alcohol 300 ppm of 40 ° C., 60 RH% gas is vented to isopropyl alcohol. In the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C., which is 1/7 of the air volume, is continuously vented to desorb isopropyl alcohol. The isopropyl alcohol removal rate was measured.

(Comparative Example 1)
After adding 160 mL of methanol to 4.8 g of nickel chloride (II) hexahydrate and stirring at room temperature for 15 minutes, 3.3 g of N, N-bis (2-aminoethyl) -1,3-propanediamine, p- Xylenediamine 1.4 g and 37% formaldehyde aqueous solution 7.2 g were added and stirred at room temperature for 30 minutes. The mixed solution was refluxed for 5 days, cooled to room temperature, and the powder was taken out from the suction filtration. The powder was thoroughly washed with methanol and then vacuum dried at 60 ° C. to obtain a nickel complex derivative.
7 mL of water was added to 0.6 g of the nickel complex derivative and stirred for 30 minutes at room temperature, and 5 mL of an aqueous solution in which 0.4 g of trimesic acid and 0.2 g of sodium hydroxide were dissolved was stirred for 30 minutes at room temperature and added dropwise. Further, 6.6 mL of dimethyl sulfoxide and 3.3 mL of pyridine were added and heated at 110 ° C. for 30 minutes. The reaction solution was subjected to suction filtration with a heated filter, and then the filtrate was cooled to room temperature, and the precipitated solid was taken out from the suction filtration. The solid was washed with ethanol and then vacuum dried at 60 ° C. to obtain a coordination polymer metal complex.
It was evaluated whether the 5% by weight thermal decomposition temperature of the coordination polymer metal complex in an air atmosphere was 180 ° C. or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said coordination polymer metal complex was implemented. The results are shown in Table 1.
Next, the porous material is applied to the gas treatment apparatus (FIG. 3) and is put into a part C on the line. In the adsorption operation, 300 ppm of isopropyl alcohol is passed through 40 ° C. and 60 RH% gas, and isopropyl alcohol is added. On the other hand, in the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C. with 1/7 of the air volume is vented to the air volume of the adsorption operation, and the operation of desorbing isopropyl alcohol is continuously performed. The isopropyl alcohol removal rate was measured.

(Comparative Example 2)
Under argon atmosphere, 300 mL of tetrahydrofuran was added to 4.7 g of 4,4′-dibrobiphenyl, and after stirring at −10 ° C. for 10 minutes, 18.8 mL of n-butyllithium was added dropwise. Then, after stirring for 30 minutes at -10 degreeC, 1.6 g of tetraethyl orthosilicates were dripped, and after stirring for 15 minutes at -10 degreeC, cooling was stopped and it stirred until it became room temperature. The reaction solution was poured into 3 L of water, and the powder was taken out by suction filtration. The powder was sufficiently washed with water, tetrahydrofuran and ethanol, and then vacuum dried at 110 ° C. to obtain a porous material.
It was evaluated whether the 5 wt% pyrolysis temperature of the porous material in an air atmosphere was 180 ° C or higher. Moreover, the isopropyl alcohol adsorption rate evaluation under the humidification of the said porous material was implemented. The results are shown in Table 1.
Next, the porous material is applied to the gas treatment apparatus (FIG. 3) and is put into a part C on the line. In the adsorption operation, 300 ppm of isopropyl alcohol is passed through 40 ° C. and 60 RH% gas, and isopropyl alcohol is added. On the other hand, in the desorption operation, on the other hand, in the desorption operation, the heating air of 180 ° C. with 1/7 of the air volume is vented to the air volume of the adsorption operation, and the operation of desorbing isopropyl alcohol is continuously performed. The isopropyl alcohol removal rate was measured.

According to the present invention, the porous material has excellent adsorption / desorption continuous processing ability such as heat resistance and adsorption / desorption, and excellent adsorption ability for a relatively polar substance other than water even in an environment where moisture is present. The porous carbon material which heat-processed the material and the said porous material can be obtained easily. The porous material and porous carbon material of the present invention can be suitably used as an adsorbent as described above, and can also be used as a filter for catalysts, storage materials, separation materials, separators, bioreactors, separation and concentration, etc. Can do. These may be used after being pelletized by pressure molding. The porous material and porous carbon material of the present invention can also be used as a carrier. For example, by carrying a catalyst, various malodorous components, volatile organic compounds (VOC) and the like can be adsorbed and decomposed and removed. Moreover, it can be used widely in various fields as described above, such as being usable as an electrode material.

Claims (6)

A porous material having a three-dimensional porous structure formed by covalent bonding of Si atoms and one or more compounds selected from the group consisting of the following general formulas (1), (2) and (3).
(In the formula, n is an arbitrary number of 0 to 4, and R is the same or different, hydrogen atom, halogen atom, hydroxyl group, amino group, alkoxy group, nitro group, methoxymethyl group, carbon number of 1-20. Alkyl group, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, fluoroalkyl group having 1 to 20 carbon atoms, fluoroaryl group having 6 to 20 carbon atoms, fluoroaralkyl having 7 to 20 carbon atoms In R, groups adjacent to each other at the bonding position may be bonded to each other to form a ring, and X _a represents a nitrogen atom, a carbon atom, an oxygen atom or a sulfur atom, provided that n = in 4, R takes all hydrogen atoms, and, except when X _a is a carbon atom.)
(Wherein l and m each take an arbitrary number of 0 to 4, and R is the same or different, a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms. Represents an aryl group having 20 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroaryl group having 6 to 20 carbon atoms, and a fluoroaralkyl group having 7 to 20 carbon atoms. The groups adjacent to each other at the bonding position may be optionally bonded to form a ring, and X _b and X _c are the same or different and each represents a nitrogen atom, a carbon atom, an oxygen atom or a sulfur atom. The position of Xc is not limited as long as they are in the same aromatic ring, provided that l = 4 and m = 4, R is all hydrogen atoms, and _Xb and _Xc are carbon atoms. Except in cases.)
(Wherein, o and q are each an arbitrary number of 0 to 4, p is an integer of 0 to 6, and R is the same or different, hydrogen atom, halogen atom, hydroxyl group, amino group, sulfonic acid group, carbon number An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroaryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms In R, the groups adjacent to each other in R may be bonded to each other to form a ring, and X _{d to} X _k are the same or different and are a nitrogen atom, a carbon atom, Represents an oxygen atom or a sulfur atom.)   The porous material according to claim 1, wherein a thermal decomposition temperature in an air atmosphere is 180 ° C. or higher. The porous material according to claim 1 or 2, wherein an adsorption rate of 500 ppm of isopropyl alcohol in an air atmosphere at 30 ° C and 20 RH% is 10 wt% or more. The porous carbon material obtained by heat-processing the porous material in any one of Claims 1-3 at 400-2000 degreeC.   The adsorbent containing the porous material or porous carbon material in any one of Claims 1-4. The gas processing apparatus using the adsorbent containing the porous material or porous carbon material in any one of Claims 1-4.