JP6730001B2 - Adsorbent molding - Google Patents
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- JP6730001B2 JP6730001B2 JP2015050078A JP2015050078A JP6730001B2 JP 6730001 B2 JP6730001 B2 JP 6730001B2 JP 2015050078 A JP2015050078 A JP 2015050078A JP 2015050078 A JP2015050078 A JP 2015050078A JP 6730001 B2 JP6730001 B2 JP 6730001B2
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- 239000003463 adsorbent Substances 0.000 title claims description 60
- 238000000465 moulding Methods 0.000 title description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 167
- 238000001179 sorption measurement Methods 0.000 claims description 132
- 229910052757 nitrogen Inorganic materials 0.000 claims description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 81
- 229910052799 carbon Inorganic materials 0.000 claims description 59
- 239000011148 porous material Substances 0.000 claims description 17
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 238000004458 analytical method Methods 0.000 claims description 9
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 8
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 8
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 8
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 99
- 229910021529 ammonia Inorganic materials 0.000 description 44
- 239000007789 gas Substances 0.000 description 21
- 238000002336 sorption--desorption measurement Methods 0.000 description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 19
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 17
- 230000008859 change Effects 0.000 description 14
- -1 alkaline earth metal salt Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000003795 desorption Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000002156 adsorbate Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 238000004438 BET method Methods 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 239000002734 clay mineral Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003232 water-soluble binding agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002551 biofuel Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- JRFMZTLWVBLNLM-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1.OC(=O)C1=CC=CC(C(O)=O)=C1 JRFMZTLWVBLNLM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZFACJPAPCXRZMQ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.OC(=O)C1=CC=CC=C1C(O)=O ZFACJPAPCXRZMQ-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ZWPWUVNMFVVHHE-UHFFFAOYSA-N terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=C(C(O)=O)C=C1 ZWPWUVNMFVVHHE-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Sorption Type Refrigeration Machines (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
本発明は、吸着材成形体に関する。 The present invention relates to an adsorbent molded body.
アンモニア等の吸着質を吸着又は脱着する炭素材料は、従来より種々の技術分野で利用されており、炭素材料の例として、活性炭等の多孔質材料が知られている。 Carbon materials that adsorb or desorb adsorbates such as ammonia have been conventionally used in various technical fields, and porous materials such as activated carbon are known as examples of carbon materials.
炭素多孔体は、例えば、電気化学キャパシタの電極材料、熱交換型反応器の吸着材、バイオ燃料電池の電極に酵素を担持する材料、キャニスタの吸着材、又は燃料精製設備の吸着材などとしての利用が期待されている。
具体的には、電気化学キャパシタにおける炭素多孔体は、電極（正極及び負極）の界面において、電極と電解液中のイオンとの間の反応に起因して発現する容量を利用する材料として期待される。熱交換型反応器における炭素多孔体は、吸着質の吸着反応又は脱着反応に伴う吸着熱又は脱着熱を利用する場合の材料として期待される。バイオ燃料電池における炭素多孔体は、負極側での酵素による糖の分解、又は正極側での酵素による酸素還元反応を行わせるため、負極及び正極に酵素を利用する場合の材料として期待される。キャニスタにおける炭素多孔体は、例えば自動車に搭載された場合のガソリン蒸気の吸着又は脱着を良好に行う場合の利用が考えられる。また、燃料精製設備における炭素多孔体は、燃料に含まれる不純物を吸着させて燃料を精製する材料として期待される。
The carbon porous material is used as, for example, an electrode material for an electrochemical capacitor, an adsorbent for a heat exchange reactor, a material for supporting an enzyme on an electrode for a biofuel cell, an adsorbent for a canister, or an adsorbent for a fuel refining facility. Expected to be used.
Specifically, the carbon porous body in the electrochemical capacitor is expected as a material that utilizes the capacity developed at the interface of the electrodes (positive electrode and negative electrode) due to the reaction between the electrodes and the ions in the electrolytic solution. It The carbon porous body in the heat exchange reactor is expected as a material when utilizing the heat of adsorption or desorption associated with the adsorption or desorption reaction of the adsorbate. The carbon porous body in the biofuel cell is expected as a material when the enzyme is used in the negative electrode and the positive electrode, because it causes the enzymatic decomposition of the sugar on the negative electrode side or the oxygen reduction reaction by the enzyme on the positive electrode side. The carbon porous body in the canister is considered to be used for favorably adsorbing or desorbing gasoline vapor when mounted on an automobile, for example. Further, the carbon porous body in the fuel refining facility is expected as a material for adsorbing impurities contained in the fuel to refine the fuel.
上記のうち、炭素多孔体を利用した用途例として、吸脱着反応に伴う吸着熱及び脱着熱により吸着材の温度が変化するために平衡関係が変化し、その後の吸脱着反応が阻害される結果、吸脱着量が低下することに鑑み、軸心方向が伝熱面と交差する向きに繊維状の熱伝導性材料を含め、吸着材と熱媒体との間の熱交換効率を向上させることで、吸着材における吸脱着反応の速度を向上させる技術が提案されている（例えば、特許文献１参照）。 Among the above, as an application example using the carbon porous material, the equilibrium relationship changes because the temperature of the adsorbent changes due to the heat of adsorption and desorption associated with the adsorption-desorption reaction, resulting in inhibition of the subsequent adsorption-desorption reaction In consideration of the decrease in the adsorption/desorption amount, the heat exchange efficiency between the adsorbent and the heat medium is improved by including the fibrous heat conductive material in the direction in which the axial direction intersects the heat transfer surface. A technique for improving the rate of adsorption/desorption reaction in an adsorbent has been proposed (see, for example, Patent Document 1).
吸着質の吸着又は脱着を行う反応系では、吸着質を吸着又は脱着する反応（吸脱着反応）を反復して利用する場合に、あらかじめ定められた作動領域の温度条件及び圧力条件下で一定時間内に吸着又は脱着できる吸着量又は脱着量が重要となる。 In a reaction system that adsorbs or desorbs an adsorbate, when a reaction for adsorbing or desorbing the adsorbate (adsorption-desorption reaction) is repeatedly used, the temperature and pressure conditions in a predetermined operating region are maintained for a certain period of time. The amount of adsorption or desorption that can be adsorbed or desorbed inside is important.
しかしながら、特許文献１に記載の発明のように、炭素多孔体として活性炭を用いた組成では、実際の使用条件、すなわち飽和蒸気圧に対する平衡圧力の相対圧力が比較的大きい圧力条件で使用する場合、相対圧力差に相応する吸脱着速度が得られず、結果、吸脱着量の向上が期待できない場合がある。
つまり、比表面積が比較的大きい活性炭等を使用した場合でも、吸着量又は脱着量が少なくなる場合がある。
However, in the composition using activated carbon as the carbon porous material as in the invention described in Patent Document 1, when used under actual use conditions, that is, when the relative pressure of the equilibrium pressure with respect to the saturated vapor pressure is relatively large, The adsorption/desorption rate corresponding to the relative pressure difference may not be obtained, and as a result, improvement of the adsorption/desorption amount may not be expected.
That is, even when activated carbon or the like having a relatively large specific surface area is used, the adsorption amount or desorption amount may be reduced.
本発明は、上記に鑑みなされたものであり、粉状物の成形により得られ、気体の吸着又は脱着の反応が速く、気体の吸着量及び脱着量の多い吸着材成形体を提供することを目的とし、かかる目的を達成することを課題とする。 The present invention has been made in view of the above, and is obtained by molding a powdery material, a reaction of gas adsorption or desorption is fast, and an adsorbent molded body having a large amount of adsorbed and desorbed gas is provided. The objective is to achieve such an objective.
課題を達成するための具体的手段には、以下に示す態様が含まれる。
＜１＞ 少なくとも粉状の炭素多孔体を含有し、ＩＵＰＡＣで定義されるＩＶ型に分類される窒素吸着等温線における、温度７７ケルビンでの飽和蒸気圧Ｐ０に対する平衡圧力Ｐの相対圧力Ｐ／Ｐ０が０．５及び０．８５であるときのそれぞれの窒素吸着量の差の絶対値が０．１５ｇ／ｍＬ（吸着材成形体１ミリリットル（ｍＬ）当たりのグラム数；以下同様）以上である吸着材成形体である。
Specific means for achieving the object include the following modes.
<1> Relative pressure P/of the equilibrium pressure P with respect to the saturated vapor pressure P 0 at a temperature of 77 Kelvin in a nitrogen adsorption isotherm containing at least a powdery carbon porous material and classified into IV type defined by IUPAC When the absolute value of the difference between the nitrogen adsorption amounts when P 0 is 0.5 and 0.85 is 0.15 g/mL (grams per 1 ml of adsorbent compact (mL); the same applies below) It is a certain adsorbent molded body.
＜２＞ 前記炭素多孔体は、前記窒素吸着等温線のαｓプロット解析から算出したミクロ細孔容量が、０．１ｍＬ／ｇ以下である＜１＞に記載の吸着材成形体である。 <2> The carbon porous body is the adsorbent shaped article according to <1>, wherein the micropore volume calculated from the αs plot analysis of the nitrogen adsorption isotherm is 0.1 mL/g or less.
＜３＞ 前記炭素多孔体は、ＩＵＰＡＣで定義されるＩＶ型に分類される窒素吸着等温線において、温度７７Ｋでの飽和蒸気圧Ｐ０に対する平衡圧力Ｐの相対圧力Ｐ／Ｐ０が０．５のときの窒素吸着量が５００ｃｍ３（ＳＴＰ）／ｇ以下であり、かつ、前記相対圧力Ｐ／Ｐ０が０．８５のときの窒素吸着量が６００ｃｍ３（ＳＴＰ）／ｇ以上１１００ｃｍ３（ＳＴＰ）／ｇ以下である＜１＞又は＜２＞に記載の吸着材成形体である。 <3> In the nitrogen adsorption isotherm classified into type IV defined by IUPAC, the carbon porous body has a relative pressure P/P 0 of the equilibrium pressure P to the saturated vapor pressure P 0 at a temperature of 77 K of 0.5. and the nitrogen adsorption amount is 500cm 3 (STP) / g or less when the, and the relative pressure P / P 0 is the nitrogen adsorption amount at the 0.85 600cm 3 (STP) / g or more 1100 cm 3 (STP )/G or less, the adsorbent molded article according to <1> or <2>.
＜４＞ 前記炭素多孔体は、ＢＥＴ法による比表面積が８００ｍ２／ｇ以上である＜１＞〜＜３＞のいずれか１つに記載の吸着材成形体である。 <4> The carbon porous body is the adsorbent molded body according to any one of <1> to <3>, which has a specific surface area of 800 m 2 /g or more as measured by the BET method.
＜５＞ 更に、水溶性バインダーを含有する＜１＞〜＜４＞のいずれか１つに記載の吸着材成形体である。 <5> The adsorbent shaped article according to any one of <1> to <4>, further containing a water-soluble binder.
本発明によれば、粉状物の成形により得られ、気体の吸着又は脱着の反応が速く、気体の吸着量及び脱着量の多い吸着材成形体が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the adsorbent compact which is obtained by shaping|molding a powdery substance, has quick gas adsorption or desorption reaction, and has a large amount of adsorption and desorption of gas is provided.
以下、本発明の吸着材成形体について詳細に説明する。
本発明の吸着材成形体は、少なくとも粉状の炭素多孔体を含有し、ＩＵＰＡＣで定義されるＩＶ型に分類される窒素吸着等温線における、温度７７Ｋでの飽和蒸気圧Ｐ０に対する平衡圧力Ｐの相対圧力Ｐ／Ｐ０が０．５及び０．８５であるときのそれぞれの窒素吸着量の差の絶対値を０．１５ｇ／ｍＬ以上とするものである。
Hereinafter, the adsorbent molded body of the present invention will be described in detail.
The adsorbent shaped article of the present invention contains at least a powdery carbon porous body, and has an equilibrium pressure P 0 with respect to a saturated vapor pressure P 0 at a temperature of 77 K in a nitrogen adsorption isotherm classified into type IV defined by IUPAC. When the relative pressure P/P 0 is 0.5 and 0.85, the absolute value of the difference between the nitrogen adsorption amounts is 0.15 g/mL or more.
従来より、活性炭等の炭素多孔体は、吸着質を吸着又は脱着（以下、吸脱着ともいう。）し得る材料として用いられているが、活性炭を用いた上記の特許文献１に記載の発明のように、作動領域における温度又は圧力によっては、必ずしも所期の吸着量又は脱着量（以下、吸脱着量ともいう。）が得られないことがある。
特に圧力の点では、相対圧力の比較的大きい作動領域では、その相対圧力の領域において、相対圧力差に対する吸着量差が大きく発現することが重要である。
本発明においては、成形体とした場合に、窒素吸着等温線（温度７７ケルビン，Ｋ）でみた場合の、飽和蒸気圧Ｐ０に対する平衡圧力Ｐの相対圧力Ｐ／Ｐ０が０．５及び０．８５であるときのそれぞれの吸着量の差の絶対値が所定値以上となるようにする。つまり、相対圧力が比較的大きい作動領域での吸着量の差に着目する。これにより、吸着材の密度を高く維持しつつも、相対圧力の比較的大きな作動領域において、相対圧力の変化量に対する窒素吸着量の変化量を大きくすることができるので、気体の圧力を変化させた際の気体の吸脱着速度が速くなり、かつ、吸脱着量を向上させることができる。
また、相対圧力（Ｐ／Ｐ０）が０．５及び０．８５であるとき、すなわち相対圧力が比較的大きい作動領域にあるときの吸着量の差に着目するので、吸脱着時の吸着熱及び脱着熱により吸脱着反応が阻害されることもない。
Conventionally, a carbon porous body such as activated carbon has been used as a material capable of adsorbing or desorbing an adsorbate (hereinafter, also referred to as adsorption/desorption). However, the invention of Patent Document 1 using activated carbon described above is used. As described above, the desired adsorption amount or desorption amount (hereinafter, also referred to as adsorption/desorption amount) may not always be obtained depending on the temperature or pressure in the operating region.
Particularly in terms of pressure, it is important that, in an operating region where the relative pressure is relatively large, a large difference in the adsorption amount with respect to the relative pressure difference appears in the region of the relative pressure.
In the present invention, when the molded body, the nitrogen adsorption isotherm (temperature 77 Kelvin, K) Demi cases were, relative pressure P / P 0 of equilibrium pressure P versus a saturated vapor pressure P 0 of 0.5 and 0 The absolute value of the difference between the adsorption amounts at 0.85 is set to be equal to or greater than a predetermined value. That is, attention is paid to the difference in the adsorption amount in the operating region where the relative pressure is relatively large. This makes it possible to increase the amount of change in the nitrogen adsorption amount with respect to the amount of change in the relative pressure in an operating region where the relative pressure is relatively high, while maintaining the density of the adsorbent high. The adsorbing/desorbing rate of the gas is increased and the adsorbing/desorbing amount can be improved.
Also, since the difference in the adsorption amount when the relative pressure (P/P 0 ) is 0.5 and 0.85, that is, when the relative pressure is in a relatively large operating region, the adsorption heat during adsorption/desorption is considered. Also, the adsorption/desorption reaction is not hindered by the heat of desorption.
本発明における吸着材成形体は、温度７７Ｋ（ケルビン）の定温下で相対圧力Ｐ／Ｐ０に対する窒素吸着量［ｇ／ｇもしくはｃｍ３（ＳＴＰ）／ｇ］の変化を測定した場合、図１に示すように、ＩＵＰＡＣで定義されるＩＶ型に分類される窒素吸着等温線を示す炭素材料である。ＩＶ型の窒素吸着等温線は、メソ細孔を有していることを示している。Ｐ／Ｐ０≒１である状態は、吸着質が多孔体内で凝縮していることを意味し、したがって吸着等温線は、飽和蒸気圧Ｐ０よりも低い圧力条件下で、炭素多孔体と吸着質とが相互作用して吸着、凝縮し、吸着によって吸着質の密度が気相中よりも高い状態にあることを示す。 The adsorbent molded article according to the present invention has a constant temperature of 77 K (Kelvin) and a change in the nitrogen adsorption amount [g/g or cm 3 (STP)/g] with respect to the relative pressure P/P 0 . As shown in, a carbon material showing a nitrogen adsorption isotherm classified into type IV defined by IUPAC. The type IV nitrogen adsorption isotherm shows that it has mesopores. The state of P/P 0 ≈1 means that the adsorbate is condensed in the porous body, and therefore the adsorption isotherm shows that the adsorbent isotherms with the carbon porous body under a pressure condition lower than the saturated vapor pressure P 0. It is shown that the density of the adsorbate is higher than that in the gas phase due to the interaction with the substance and adsorption and condensation.
吸着材成形体は、窒素吸着等温線において、相対圧力Ｐ／Ｐ０が０．５であるときの窒素吸着量Ａ０．５Ｎ２と、相対圧力Ｐ／Ｐ０が０．８５であるときの窒素吸着量Ａ０．８５Ｎ２と、の差の絶対値が、０．１５ｇ／ｍＬ以上である。なお、相対圧力は、飽和蒸気圧Ｐ０と平衡圧力Ｐとの相対比で表される。平衡圧力Ｐは、窒素を吸着材成形体に吸着させて、計測圧力の変化がほぼ観測されなくなった時点の圧力を平衡圧力とすることで、窒素吸着量の測定により求められる。窒素吸着量は、カンタクローム社製のＡｕｔｏｓｏｒｂ−１を用いて測定される値である。
窒素吸着量Ａ０．８５Ｎ２と窒素吸着量Ａ０．５Ｎ２との差（例えば、窒素吸着量Ａ０．８５Ｎ２−窒素吸着量Ａ０．５Ｎ２による減算値）が０．１５ｇ／ｍＬ以上であることで、メソ細孔を有する構造でありながら相対圧力の比較的大きな領域において、相対圧力の変化量に対する窒素吸着量の変化量が大きくなる。そのため、特定の気体に対して、気体圧力を変化させた場合の気体の吸脱着量を向上させることができる。
窒素吸着量Ａ０．８５Ｎ２と窒素吸着量Ａ０．５Ｎ２との差は、相対圧力の変化量に対する窒素吸着量の変化量を高める観点から、大きいほど望ましく、０．２ｇ／ｍＬ以上が好ましく、０．３ｇ／ｍＬ以上がより好ましく、０．４ｇ／ｍＬ以上が更に好ましく、０．５ｇ／ｍＬ以上が更に好ましく、０．６ｇ／ｍＬ以上が特に好ましい。
In the nitrogen adsorption isotherm, the adsorbent molded body has a nitrogen adsorption amount A 0.5N2 at a relative pressure P/P 0 of 0.5 and nitrogen at a relative pressure P/P 0 of 0.85. The absolute value of the difference between the adsorption amount A 0.85N2 and the adsorption amount A is 0.15 g/mL or more. The relative pressure is represented by the relative ratio between the saturated vapor pressure P 0 and the equilibrium pressure P. The equilibrium pressure P is obtained by measuring the amount of adsorbed nitrogen by adsorbing nitrogen to the adsorbent molded body and setting the pressure when the change in the measured pressure is almost not observed as the equilibrium pressure. The nitrogen adsorption amount is a value measured using Autosorb-1 manufactured by Cantachrome.
The difference between the nitrogen adsorption A 0.85N2 and nitrogen adsorption A 0.5N2 (e.g., nitrogen adsorption A 0.85N2 - subtraction value by nitrogen adsorption A 0.5N2) is not less than 0.15 g / mL Thus, in a region where the structure has mesopores and the relative pressure is relatively large, the change amount of the nitrogen adsorption amount with respect to the change amount of the relative pressure becomes large. Therefore, it is possible to improve the adsorption/desorption amount of the gas when the gas pressure is changed with respect to the specific gas.
The difference between the nitrogen adsorption amount A 0.85N2 and the nitrogen adsorption amount A 0.5N2 is preferably as large as possible from the viewpoint of increasing the change amount of the nitrogen adsorption amount with respect to the change amount of the relative pressure, and is preferably 0.2 g/mL or more, 0.3 g/mL or more is more preferable, 0.4 g/mL or more is further preferable, 0.5 g/mL or more is further preferable, and 0.6 g/mL or more is particularly preferable.
窒素吸着量Ａ０．８５Ｎ２と窒素吸着量Ａ０．５Ｎ２との差は、以下の方法で求められる。
例えばアンモニアを吸着材成形体に吸着させ、温度２７３ケルビンで相対圧力Ｐ／Ｐ０を変化させた際に吸着材成形体１ｇに吸着するアンモニアの吸着量［ｇ／ｇ］を測定する。測定値に基づき、相対圧力Ｐ／Ｐ０を横軸にとり、炭素多孔体１ｇに吸着したアンモニア吸着量［ｇ／ｇ］を縦軸にとってプロットし、温度２７３ケルビンでの飽和蒸気圧Ｐ０に対する平衡圧力Ｐの相対圧力Ｐ／Ｐ０とアンモニア吸着量との関係線（吸着等温線）を作成する。この関係線（吸着等温線）より、相対圧力Ｐ／Ｐ０の差に対するアンモニア吸着量差を求めることができる。
ここで、同様に温度７７ケルビンで窒素を吸着させた場合の相対圧力Ｐ／Ｐ０と窒素吸着量との関係線（吸着等温線）を作成した場合、図２に示すように、求められるアンモニア吸着量差と窒素吸着量差とには直線的な相関関係がある。
したがって、アンモニア吸着量差と窒素吸着量差との間の相関関係に基づいて、相対圧力Ｐ／Ｐ０の差に対するアンモニア吸着量差から、相対圧力Ｐ／Ｐ０の差に対する窒素吸着量差を求めることができる。
The difference between the nitrogen adsorption amount A 0.85N2 and the nitrogen adsorption amount A 0.5N2 is obtained by the following method.
For example, ammonia is adsorbed on the adsorbent compact, and when the relative pressure P/P 0 is changed at a temperature of 273 Kelvin, the adsorbed amount [g/g] of ammonia adsorbed on the adsorbent compact 1 g is measured. Based on the measured values, the relative pressure P / P 0 the horizontal axis, the ammonia adsorption amount adsorbed to the porous carbon material 1g of [g / g] plotted ordinate, the equilibrium for the saturated vapor pressure P 0 at the temperature 273 Kelvin A relation line (adsorption isotherm) between the relative pressure P/P 0 of the pressure P and the ammonia adsorption amount is created. From this relational line (adsorption isotherm), the difference in the amount of adsorbed ammonia with respect to the difference in relative pressure P/P 0 can be determined.
Here, similarly, when a relational line (adsorption isotherm) between the relative pressure P/P 0 and the nitrogen adsorption amount when nitrogen is adsorbed at a temperature of 77 Kelvin is created, as shown in FIG. There is a linear correlation between the adsorption amount difference and the nitrogen adsorption amount difference.
Therefore, based on the correlation between the ammonia adsorption amount difference and the nitrogen adsorption amount difference, the ammonia adsorption amount difference for the difference of the relative pressure P / P 0, the nitrogen adsorption amount difference for the difference of the relative pressure P / P 0 You can ask.
（炭素多孔体）
本発明の吸着材成形体は、炭素材料として、粉状の炭素多孔体の少なくとも一種を含む。粉状の炭素多孔体を含むことで、成形体とした場合に多孔構造が得られ、気体の吸着サイトとなる比表面積を大きくとることができる。
かかる観点から、炭素多孔体は、メソ細孔を有する多孔体が好ましい。
(Carbon porous material)
The adsorbent shaped body of the present invention contains at least one kind of powdery carbon porous body as a carbon material. By including the powdery carbon porous body, a porous structure can be obtained in the case of forming a molded body, and a large specific surface area serving as a gas adsorption site can be obtained.
From this viewpoint, the carbon porous body is preferably a porous body having mesopores.
窒素吸着量Ａ０．８５Ｎ２及び窒素吸着量Ａ０．５Ｎ２の差が０．１５ｇ／ｍｌ以上である吸着材成形体に好適な炭素多孔体としては、窒素吸着等温線のαｓプロット解析から算出したミクロ細孔容量が、０．１ｍＬ／ｇ以下である炭素多孔体が好ましい。 The carbon porous body suitable for the adsorbent shaped article having a difference between the nitrogen adsorption amount A 0.85N2 and the nitrogen adsorption amount A 0.5N2 of 0.15 g/ml or more was calculated from the αs plot analysis of the nitrogen adsorption isotherm. A carbon porous body having a micropore volume of 0.1 mL/g or less is preferable.
上記の窒素吸着等温線のαｓプロット解析では、プロット外挿直線の切片の値により、ミクロ細孔容量（ｍＬ／ｇ）を求めた。αｓプロット解析では、相対圧力が０．４の吸着量を基準にαｓ値を算出して吸着等温線を解析する。ミクロ細孔容量（ｍＬ／ｇ）は、標準ガス体積（ｃｍ３（ＳＴＰ）／ｇ）を７７ケルビンの液体窒素密度（０．８０８ｇ／ｃｍ３）を用いて変換した値である。なお、αｓプロット解析では、比較用の標準等温線として、 "Characterizaton of porous carbons with high resolusion alpha(s) -analysis and low temperature magnetic susceptibility" Kaneko, K; Ishii, C; Kanoh, H; Hanzawa, Y; Setoyama, N; Suzuki, T. ADVANCES IN COLLOID AND INTERFACE SCIENCE vo.76, p295-320(1998) に記載された標準等温線を用いた。 In the αs plot analysis of the above nitrogen adsorption isotherm, the micropore volume (mL/g) was obtained from the value of the intercept of the plot extrapolation line. In the αs plot analysis, the adsorption isotherm is analyzed by calculating the αs value based on the adsorption amount having a relative pressure of 0.4. The micropore volume (mL/g) is a value obtained by converting the standard gas volume (cm 3 (STP)/g) using a liquid nitrogen density of 77 Kelvin (0.808 g/cm 3 ). In the αs plot analysis, "Characterizaton of porous carbons with high resolusion alpha(s) -analysis and low temperature magnetic susceptibility" Kaneko, K; Ishii, C; Kanoh, H; Hanzawa, Y Setoyama, N; Suzuki, T. ADVANCES IN COLLOID AND INTERFACE SCIENCE vo.76, p295-320 (1998).
メソ細孔を有する炭素多孔体としては、ＢＥＴ法による比表面積（ＢＥＴ比表面積）が８００ｍ2／ｇ以上であることが好ましく、１０００ｍ2／ｇ以上がより好ましく、１２００ｍ2／ｇ以上が更に好ましい。比表面積の大きさが、各種機能特性の向上に相関があるためである。 As the carbon porous body having mesopores, the specific surface area by BET method (BET specific surface area) is preferably 800 m 2 /g or more, more preferably 1000 m 2 /g or more, still more preferably 1200 m 2 /g or more. .. This is because the size of the specific surface area has a correlation with the improvement of various functional characteristics.
ＢＥＴ比表面積は、ＢＥＴ法によって単位質量あたりの表面積として求められる比表面積（ｍ２／ｇ）のことである。
ＢＥＴ比表面積は、窒素（Ｎ２）分子を炭素多孔体に吸着させ、吸着したＮ２分子の量から求められる。すなわち、圧力（Ｐ）とＮ２吸着量（Ｖ）との関係から、ＢＥＴ法（
Brunauer, Emmet and Teller's equation）により炭素多孔体の表面に吸着したＮ２分子の単分子吸着量（Ｖｍ）を求め、下記式から算出される値である。
比表面積 ＝（Ｖｍ×Ｎ／Ｍ）×Ａｍ 〔Ａｍ：分子１つあたりの占有面積〕
ＢＥＴプロットの直線領域は、相対圧力Ｐ／Ｐ０で０．０５〜０．３の範囲を採用して、上記Ｖｍを決定する。
The BET specific surface area is a specific surface area (m 2 /g) obtained as a surface area per unit mass by the BET method.
The BET specific surface area is obtained by adsorbing nitrogen (N 2 ) molecules on the porous carbon body and determining the amount of the adsorbed N 2 molecules. That is, from the relationship between the pressure (P) and the N 2 adsorption amount (V), the BET method (
Brunauer, Emmet and Teller's equation) is used to obtain the monomolecular adsorption amount (Vm) of N 2 molecules adsorbed on the surface of the carbon porous body, which is a value calculated from the following formula.
Specific surface area = (Vm x N/M) x Am [Am: occupied area per molecule]
The linear region of the BET plot adopts the range of 0.05 to 0.3 in relative pressure P/P 0 to determine the above Vm.
上記の中でも、窒素吸着等温線のαｓプロット解析から算出したミクロ細孔容量が０．１ｍＬ／ｇ以下であり、かつ、ＢＥＴ比表面積）が８００ｍ2／ｇ以上である炭素多孔体がより好ましい。 Among the above, a carbon porous body having a micropore volume of 0.1 mL/g or less and a BET specific surface area) of 800 m 2 /g or more calculated from αs plot analysis of nitrogen adsorption isotherm is more preferable.
更には、炭素多孔体は、相対圧力の変化量に対する窒素吸着量の変化量が大きい点で、ＩＵＰＡＣで定義されるＩＶ型に分類される窒素吸着等温線において、温度７７Ｋでの飽和蒸気圧Ｐ０に対する平衡圧力Ｐの相対圧力Ｐ／Ｐ０が０．５のときの窒素吸着量が５００ｃｍ３（ＳＴＰ）／ｇ以下であり、かつ、前記相対圧力Ｐ／Ｐ０が０．８５のときの窒素吸着量が６００ｃｍ３（ＳＴＰ）／ｇ以上１１００ｃｍ３（ＳＴＰ）／ｇ以下であることが好ましい。
この場合、相対圧力Ｐ／Ｐ０が０．８５のときの窒素吸着量から相対圧力Ｐ／Ｐ０が０．５のときの窒素吸着量を差し引いた値が１００ｃｍ３（ＳＴＰ）／ｇ以上６００ｃｍ３（ＳＴＰ）／ｇ以下になる。そのため、相対圧力の比較的大きな領域において、相対圧力の変化量に対する窒素吸着量の変化量をより大きくすることができる。よって、気体の圧力を変化させたときの気体の吸脱着量は更に大きくなる。
Further, the carbon porous body has a large change in the amount of adsorbed nitrogen with respect to the amount of change in the relative pressure, and in the nitrogen adsorption isotherm classified into type IV defined by IUPAC, the saturated vapor pressure P at a temperature of 77K is When the relative pressure P/P 0 of the equilibrium pressure P with respect to 0 is 0.5 cm 3 (STP)/g or less when the relative pressure P/P 0 is 0.5 and the relative pressure P/P 0 is 0.85. The nitrogen adsorption amount is preferably 600 cm 3 (STP)/g or more and 1100 cm 3 (STP)/g or less.
In this case, the value obtained by subtracting the nitrogen adsorption amount when the relative pressure P/P 0 is 0.5 from the nitrogen adsorption amount when the relative pressure P/P 0 is 0.85 is 100 cm 3 (STP)/g or more and 600 cm or more. 3 (STP)/g or less. Therefore, in a region where the relative pressure is relatively large, the amount of change in the nitrogen adsorption amount with respect to the amount of change in the relative pressure can be increased. Therefore, the amount of adsorption and desorption of gas when the pressure of gas is changed is further increased.
なお、本明細書中において、「ＳＴＰ」は、標準温度圧力（０℃，１ａｔｍ）のことであり、「ｃｍ３（ＳＴＰ）／ｇ」は、炭素多孔体１ｇあたりの標準温度圧力での量（標準ガス体積；＝ｍＬ）を表す。 The amount of in this specification, "STP" is standard temperature and pressure (0 ° C., 1 atm) and that of "cm 3 (STP) / g" is a standard temperature and pressure per carbon porous body 1g (Standard gas volume; = mL).
炭素多孔体としては、以下に示す製造方法により得られる多孔体が好ましい。以下の製造方法は、上記の細孔容量及びＢＥＴ比表面積、並びに相対圧力Ｐ／Ｐ０が０．５及び０．８５のときの上記窒素吸着量を満たす炭素多孔体が得られる点で好ましい。
具体的には、本発明に好適な態様の炭素多孔体は、ベンゼンジカルボン酸のアルカリ土類金属塩を不活性雰囲気中で５５０℃〜７００℃の温度で加熱して炭素とアルカリ土類金属炭酸塩との複合体を形成し、形成された複合体を、アルカリ土類金属炭酸塩を溶解可能な洗浄液により洗浄し、アルカリ土類金属炭酸塩を除去することによって、粉状物として得られる炭素多孔体である。
As the carbon porous body, a porous body obtained by the following production method is preferable. The following production method is preferable in that a carbon porous body satisfying the above-mentioned pore volume and BET specific surface area and the above nitrogen adsorption amount when the relative pressure P/P 0 is 0.5 and 0.85 can be obtained.
Specifically, the carbon porous body of a preferred embodiment of the present invention is obtained by heating an alkaline earth metal salt of benzenedicarboxylic acid at a temperature of 550° C. to 700° C. in an inert atmosphere and carbon and an alkaline earth metal carbonate. Carbon which is obtained as a powder by forming a complex with a salt, washing the formed complex with a washing solution capable of dissolving an alkaline earth metal carbonate, and removing the alkaline earth metal carbonate. It is a porous body.
ベンゼンジカルボン酸としては、例えば、フタル酸（ベンゼン−１，２−ジカルボン酸）、イソフタル酸（ベンゼン−１，３−ジカルボン酸）、テレフタル酸（ベンゼン−１，４−ジカルボン酸）などが挙げられ、中でも、テレフタル酸が好ましい。
アルカリ土類金属としては、マグネシウム、カルシウム、ストロンチウム、バリウムなどが挙げられ、中でも、カルシウムが好ましい。
ベンゼンジカルボン酸のアルカリ土類金属塩は、上市されている市販品を用いてもよいし、ベンゼンジカルボン酸とアルカリ土類金属の水酸化物とを水中で混合することにより合成してもよい。合成する場合、ベンゼンジカルボン酸とアルカリ土類金属の水酸化物とのモル比は、中和反応式に基づく化学量論量だけを用いてもよいし、一方が他方に対して過剰になるように用いてもよい。例えば、ベンゼンジカルボン酸とアルカリ土類金属の水酸化物とのモル比は、１．５：１〜１：１．５の範囲で選択することができる。
ベンゼンジカルボン酸とアルカリ土類金属の水酸化物とを水中で混合する場合、５０℃〜１００℃に加熱してもよい。
Examples of benzenedicarboxylic acid include phthalic acid (benzene-1,2-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), terephthalic acid (benzene-1,4-dicarboxylic acid), and the like. Among them, terephthalic acid is preferable.
Examples of the alkaline earth metal include magnesium, calcium, strontium, and barium, and among them, calcium is preferable.
As the alkaline earth metal salt of benzenedicarboxylic acid, a commercially available product on the market may be used, or it may be synthesized by mixing benzenedicarboxylic acid and a hydroxide of alkaline earth metal in water. When synthesizing, the molar ratio of benzenedicarboxylic acid to hydroxide of alkaline earth metal may be a stoichiometric amount based on the neutralization reaction formula, or one may be in excess with respect to the other. May be used for. For example, the molar ratio of benzenedicarboxylic acid and hydroxide of alkaline earth metal can be selected in the range of 1.5:1 to 1:1.5.
When benzenedicarboxylic acid and the hydroxide of an alkaline earth metal are mixed in water, you may heat at 50 degreeC-100 degreeC.
炭素多孔体を製造する場合の不活性雰囲気としては、窒素雰囲気、アルゴン雰囲気などが挙げられる。 Examples of the inert atmosphere for producing the carbon porous body include a nitrogen atmosphere and an argon atmosphere.
また、製造時の加熱温度は、５５０℃〜７００℃の範囲とすることが好ましい。
加熱温度が５５０℃以上であると、７７Ｋでの窒素吸着等温線の相対圧力Ｐ／Ｐ0が０．８５のときの窒素吸着量を向上させることができる。加熱温度を７００℃以下に抑えることで、炭素多孔体の製造を好適に行うことができる。
In addition, the heating temperature during manufacturing is preferably in the range of 550°C to 700°C.
When the heating temperature is 550° C. or higher, the nitrogen adsorption amount can be improved when the relative pressure P/P 0 of the nitrogen adsorption isotherm at 77K is 0.85. By controlling the heating temperature to 700° C. or lower, the carbon porous body can be preferably manufactured.
加熱後に得られる炭素とアルカリ土類金属炭酸塩との複合体は、層状炭化物の層間にアルカリ土類金属炭酸塩が入り込んだ構造を有するものと推定される。
そして、形成された複合体は、アルカリ土類金属炭酸塩を溶解可能な洗浄液により洗浄される。洗浄することにより、複合体中のアルカリ土類金属炭酸塩が存在していた箇所が空洞になるものと推定される。
The composite of carbon and alkaline earth metal carbonate obtained after heating is presumed to have a structure in which the alkaline earth metal carbonate enters between the layers of the layered carbide.
Then, the formed complex is washed with a washing liquid capable of dissolving the alkaline earth metal carbonate. It is presumed that by washing, the place where the alkaline earth metal carbonate was present in the complex becomes hollow.
アルカリ土類金属炭酸塩を溶解可能な洗浄液としては、例えば、アルカリ土類金属炭酸塩が炭酸カルシウムの場合は水又は酸性水溶液が好ましい。酸性水溶液としては、例えば、塩酸、硝酸、及び酢酸などの水溶液が挙げられる。 As the cleaning liquid capable of dissolving the alkaline earth metal carbonate, for example, water or an acidic aqueous solution is preferable when the alkaline earth metal carbonate is calcium carbonate. Examples of the acidic aqueous solution include aqueous solutions of hydrochloric acid, nitric acid, acetic acid and the like.
吸着材成形体中における炭素多孔体の充填密度としては、０．１０ｇ／ｍＬ〜０．８０ｇ／ｍＬが好ましく、０．２０ｇ／ｍＬ〜０．５０ｇ／ｍＬがより好ましい。充填密度が０．１０ｇ／ｍＬ以上であると、吸脱着反応に関与する吸着質の量をより多くすることができる。充填密度が０．８０ｇ／ｍＬ以下であると、吸着材成形体中における吸着質の移動抵抗をより低減できる。 The packing density of the carbon porous material in the adsorbent shaped body is preferably 0.10 g/mL to 0.80 g/mL, more preferably 0.20 g/mL to 0.50 g/mL. When the packing density is 0.10 g/mL or more, the amount of adsorbate involved in the adsorption/desorption reaction can be increased. When the packing density is 0.80 g/mL or less, the migration resistance of the adsorbate in the adsorbent compact can be further reduced.
（他の成分）
本発明の吸着材成形体は、上記の炭素多孔体に加え、例えば、バインダー、造孔材、又は添加剤等の他の成分を含有してもよい。また、本発明の効果を損なわない範囲内において、上記の炭素多孔体以外の吸着材を更に含有してもよい。
(Other ingredients)
The adsorbent shaped article of the present invention may contain other components such as a binder, a pore former, or an additive, in addition to the carbon porous body. Further, an adsorbent other than the above-mentioned carbon porous body may be further contained within a range that does not impair the effects of the present invention.
本発明の吸着材成形体は、バインダーの少なくとも一種を含有することが好ましい。
バインダーとしては、水溶性バインダーの少なくとも１種が好ましい。水溶性バインダーとしては、ポリビニルアルコール、トリメチルセルロース、ヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、カルボキシメチルセルロース（ＣＭＣ）等が挙げられる。中でも、ヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、トリメチルセルロースが好ましい。
The adsorbent shaped article of the present invention preferably contains at least one binder.
As the binder, at least one water-soluble binder is preferable. Examples of the water-soluble binder include polyvinyl alcohol, trimethyl cellulose, hydroxypropyl methyl cellulose (HPMC), carboxymethyl cellulose (CMC) and the like. Of these, hydroxypropylmethyl cellulose (HPMC) and trimethyl cellulose are preferable.
バインダーを含む場合、バインダーの含有量は、吸着材成形体の全質量に対して、１質量％〜２０質量％の範囲が好ましく、１質量％〜１０質量％の範囲がより好ましい。 When a binder is included, the content of the binder is preferably in the range of 1% by mass to 20% by mass, more preferably in the range of 1% by mass to 10% by mass, based on the total mass of the adsorbent shaped body.
上記の炭素多孔体以外の吸着材としては、例えば、活性炭、メソポーラスシリカ、ゼオライト、シリカゲル、粘土鉱物等が挙げられる。粘土鉱物は、非架橋の粘土鉱物であっても、架橋された粘土鉱物（架橋粘土鉱物）であってもよく、例えば、セピオライト、スメクタイト系粘土（サポナイト、モンモリロナイト、ヘクトライト、等）、４−珪素雲母、雲母、バーミキュライト等が挙げられる。 Examples of the adsorbent other than the above-mentioned carbon porous material include activated carbon, mesoporous silica, zeolite, silica gel, clay minerals and the like. The clay mineral may be a non-crosslinked clay mineral or a crosslinked clay mineral (crosslinked clay mineral), and examples thereof include sepiolite, smectite clay (saponite, montmorillonite, hectorite, etc.), 4- Examples thereof include silicon mica, mica, vermiculite and the like.
本発明の吸着材成形体は、以下の方法で作製することができる。
本発明の吸着材成形体の製造は、特に制限はなく、既述の炭素多孔体及び必要に応じて熱伝導性材料を含む混合物（例えばスラリー）を調製し、調製された混合物を公知の成形手段により成形することによって行うことができる。
成形手段としては、加圧成形、押出成形等を目的等に応じて適宜選択することができる。
The adsorbent molded body of the present invention can be manufactured by the following method.
The production of the adsorbent shaped article of the present invention is not particularly limited, and a mixture (for example, a slurry) containing the above-mentioned carbon porous body and optionally a heat conductive material is prepared, and the prepared mixture is formed into a known shape. It can be performed by molding by means.
As the molding means, pressure molding, extrusion molding or the like can be appropriately selected according to the purpose and the like.
成形時の圧力は、目的とする成形物の成形が行えればよく、例えば０．５ＭＰａ〜１００ＭＰａの範囲である。 The pressure at the time of molding may be any pressure as long as the desired molded product can be molded, and is in the range of 0.5 MPa to 100 MPa, for example.
また、熱伝導性材料を含有する吸着材成形体を作製する場合、既述のようなアスペクト比を有する繊維状の熱伝導性材料を伝熱面（吸脱着反応面）に対して所定の角度で含有させる方法は、特に制限はないが、例えば特開２０１４−０４４０００号公報に記載の方法にて行うことができる。 Further, when an adsorbent molded body containing a heat conductive material is produced, a fibrous heat conductive material having an aspect ratio as described above is formed at a predetermined angle with respect to the heat transfer surface (adsorption/desorption reaction surface). There is no particular limitation on the method of incorporating the above-mentioned compound. However, for example, the method described in JP-A-2014-044000 can be used.
本発明の吸着材成形体は、例えば、気体のアンモニアを吸着又は脱着する吸着材料として利用することができる。
作動領域において、アンモニア圧力が３９０ｋＰａのときのアンモニア吸着量Ａ３９ＮＨ３と、アンモニア圧力が３００ｋＰａのときのアンモニア吸着量Ａ３０ＮＨ３と、の差の絶対値（例えば、アンモニア吸着量Ａ３９ＮＨ３−アンモニア吸着量Ａ３０ＮＨ３による減算値）が、０．４０ｇ／ｇ以上であることが好ましい。
この場合、窒素吸着させた場合の吸着量差と、アンモニア吸着させた場合の吸着量差と、を求め、二次元座標上にプロットすると、図２に示す直線的な相関関係が得られる。図２に示す相関関係から、窒素吸着量Ａ０．８５Ｎ２及び窒素吸着量Ａ０．５Ｎ２の差としての好ましい範囲は、４００ｃｍ３（ＳＴＰ）／ｇ以上となる。
アンモニア圧力を作動領域の圧力に合わせて調節することにより、アンモニアの吸脱着速度を速めることができ、ひいては多量のアンモニアを吸着又は脱着できる。これにより、アンモニアガスの吸脱着量は向上する。
The adsorbent molded body of the present invention can be used as an adsorbent material that adsorbs or desorbs gaseous ammonia, for example.
In the operating region, the absolute value of the difference between the ammonia adsorption amount A 39NH3 when the ammonia pressure is 390 kPa and the ammonia adsorption amount A 30NH3 when the ammonia pressure is 300 kPa (for example, ammonia adsorption amount A 39NH3 − ammonia adsorption amount A 39NH3 − It is preferable that the subtraction value by 30NH3 ) is 0.40 g/g or more.
In this case, when the difference in adsorption amount when nitrogen is adsorbed and the difference in adsorption amount when ammonia is adsorbed are plotted and plotted on the two-dimensional coordinates, the linear correlation shown in FIG. 2 is obtained. From the correlation shown in FIG. 2, the preferable range of the difference between the nitrogen adsorption amount A 0.85N2 and the nitrogen adsorption amount A 0.5N2 is 400 cm 3 (STP)/g or more.
By adjusting the ammonia pressure according to the pressure in the operation region, the adsorption/desorption rate of ammonia can be increased, and thus a large amount of ammonia can be adsorbed or desorbed. As a result, the adsorption/desorption amount of ammonia gas is improved.
以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」は質量基準である。 Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, "part" is based on mass unless otherwise specified.
（実施例１）
−炭素多孔体の作製−
（１．テレフタル酸のカルシウム塩の合成）
テレフタル酸（０．１ｍｏｌ）と水酸化カルシウム（０．１ｍｏｌ）とを水２００ｍＬ中に加え、８０℃の水浴で４時間加熱した。加熱後、生成したテレフタル酸のカルシウム塩の結晶を濾過して分取し、室温で風乾した。
(Example 1)
-Preparation of carbon porous body-
(1. Synthesis of calcium salt of terephthalic acid)
Terephthalic acid (0.1 mol) and calcium hydroxide (0.1 mol) were added to 200 mL of water and heated in a water bath at 80° C. for 4 hours. After heating, the formed crystals of calcium salt of terephthalic acid were collected by filtration and air dried at room temperature.
（２．テレフタル酸のカルシウム塩の炭素化）
テレフタル酸のカルシウム塩４ｇを管状電気炉内に配置し、管状電気炉内に窒素ガス（不活性ガス）を０．１Ｌ／分の流速で流し、炉内をガスフロー置換した。ガスフローを維持したまま、炉内温度を５５０℃（設定温度）まで１時間かけて昇温した。昇温完了後、ガスフローを維持したまま、５５０℃で２時間保持し、２時間経過後に室温（２５℃）まで冷却した。炉内に、炭素と炭酸カルシウム（アルカリ土類金属炭酸塩）との複合体を生成した。
(2. Carbonization of calcium salt of terephthalic acid)
4 g of calcium salt of terephthalic acid was placed in a tubular electric furnace, and nitrogen gas (inert gas) was flown in the tubular electric furnace at a flow rate of 0.1 L/min to replace the gas flow in the furnace. While maintaining the gas flow, the temperature inside the furnace was raised to 550° C. (set temperature) over 1 hour. After the temperature was raised, the temperature was maintained at 550° C. for 2 hours while maintaining the gas flow, and after 2 hours, the temperature was cooled to room temperature (25° C.). A complex of carbon and calcium carbonate (alkaline earth metal carbonate) was formed in the furnace.
（３．複合体の酸処理）
続いて、複合体を電気炉から取り出し、水５００ｍＬに分散させた。分散液に２ｍｏｌ／Ｌの塩酸５０ｍＬを添加し、撹拌した。その後、炭酸カルシウムの分解によると思われる発泡が観察された。次いで、分散液を濾過し、濾物を乾燥させた。
以上のようにして、目的とする粉末状の炭素多孔体を得た（収量：約１ｇ）。なお、ミクロ細孔容量は、窒素吸着等温線のαｓプロット解析から算出した。
(3. Acid treatment of complex)
Subsequently, the composite was taken out of the electric furnace and dispersed in 500 mL of water. 50 mL of 2 mol/L hydrochloric acid was added to the dispersion and stirred. After that, foaming was observed, which is probably due to the decomposition of calcium carbonate. Then, the dispersion liquid was filtered, and the residue was dried.
Thus, the desired powdery carbon porous material was obtained (yield: about 1 g). The micropore volume was calculated from the αs plot analysis of the nitrogen adsorption isotherm.
（４．炭素多孔体の特性）
得られた炭素多孔体の特性を以下の方法で求めた。結果を下記表１に示す。
（４−１）窒素吸着量Ａ０．５Ｎ２，Ａ０．８５Ｎ２の算出
得られた炭素多孔体を用い、温度７７Ｋで窒素を炭素多孔体に吸着させた。測定は、カンタクローム社製Ａｕｔｏｓｏｒｂ−１を用いて行い、相対圧力Ｐ／Ｐ０を横軸とし、窒素吸着量［ｃｍ３（ＳＴＰ）／ｇ］を縦軸として吸着等温線を作成した。この吸着等温線より、相対圧力Ｐ／Ｐ０が０．５及び０．８５のときの窒素吸着量Ａ０．５Ｎ２，Ａ０．８５Ｎ２の値を窒素吸着等温線から読み取り、両者の差（＝Ａ０．５Ｎ２−Ａ０．８５Ｎ２）を算出した。
（４−２）アンモニア吸着量Ａ３９ＮＨ３，Ａ３０ＮＨ３の算出
得られた炭素多孔体を用い、温度２７３Ｋにてアンモニアを炭素多孔体に吸着させた。飽和蒸気圧Ｐ０は、４３０ｋＰａであった。圧力Ｐを変化させた際の炭素多孔体１ｇに吸着するアンモニアの吸着量［ｇ／ｇ］を測定し、圧力Ｐ［ｋＰａ］を横軸とし、炭素多孔体１ｇに吸着したアンモニア吸着量［ｇ／ｇ］を縦軸として吸着等温線を作成した。この吸着等温線より、アンモニア圧力が３９０ｋＰａのときのアンモニア吸着量Ａ３９ＮＨ３、及びアンモニア圧力が３００ｋＰａのときのアンモニア吸着量Ａ３０ＮＨ３を読み取り、両者の差（＝Ａ３９ＮＨ３−Ａ３０ＮＨ３）を算出した。
（４−３）ＢＥＴ比表面積の算出
窒素（Ｎ２）分子を炭素多孔体に吸着させ、吸着したＮ２分子の量に基づいてＢＥＴ法により単位質量あたりの表面積（ｍ２／ｇ）を求めた。
(4. Characteristics of carbon porous material)
The characteristics of the obtained carbon porous material were determined by the following methods. The results are shown in Table 1 below.
(4-1) Calculation of nitrogen adsorption amount A 0.5N2 , A 0.85N2 Using the obtained carbon porous body, nitrogen was adsorbed on the carbon porous body at a temperature of 77K. The measurement was performed using Autosorb-1 manufactured by Kantachrome Co., Ltd., and an adsorption isotherm was created with the relative pressure P/P 0 as the horizontal axis and the nitrogen adsorption amount [cm 3 (STP)/g] as the vertical axis. From this adsorption isotherm, the values of the nitrogen adsorption amounts A 0.5N2 and A 0.85N2 at relative pressures P/P 0 of 0.5 and 0.85 were read from the nitrogen adsorption isotherm, and the difference (= A 0.5N2- A 0.85N2 ) was calculated.
(4-2) Calculation of Ammonia Adsorption A39NH3 , A30NH3 Using the obtained carbon porous body, ammonia was adsorbed on the carbon porous body at a temperature of 273K . The saturated vapor pressure P 0 was 430 kPa. The adsorption amount [g/g] of ammonia adsorbed on the carbon porous body 1g when the pressure P was changed was measured, and the ammonia adsorption amount [g]g adsorbed on the carbon porous body 1g was measured with the pressure P [kPa] as the horizontal axis. /G] was used as the vertical axis to create an adsorption isotherm. From this adsorption isotherm, the ammonia adsorption amount A 39NH3 when the ammonia pressure was 390 kPa and the ammonia adsorption amount A 30NH3 when the ammonia pressure was 300 kPa were read, and the difference between them (=A 39NH3- A 30NH3 ) was calculated.
(4-3) Calculation of BET Specific Surface Area Nitrogen (N 2 ) molecules are adsorbed on the carbon porous body, and the surface area per unit mass (m 2 /g) is determined by the BET method based on the amount of the adsorbed N 2 molecules. It was
−吸着材成形体の作製−
上記で得た粉末状の炭素多孔体１００部及びヒドロキシプロピルメチルセルロース（ＨＰＭＣ；水溶性バインダー）１１部に、水３００部を徐々に添加しながら混練し、スラリーを調製した。調製したスラリーを１５ｍｍ×１５ｍｍの金型に詰め、油圧式ハンドプレスを用いて３．１ＭＰａで加圧して成形処理し、吸着材成形体を作製した。
-Preparation of adsorbent molded body-
A slurry was prepared by kneading 100 parts of the powdery carbonaceous material obtained above and 11 parts of hydroxypropylmethylcellulose (HPMC; water-soluble binder) while gradually adding 300 parts of water. The prepared slurry was packed in a metal mold of 15 mm×15 mm, and pressed by a hydraulic hand press at 3.1 MPa to carry out a molding treatment to produce an adsorbent molded body.
次いで、得られた吸着材成形体を８０℃で乾燥し、乾燥後の外寸をノギスで測定した。乾燥後の乾燥重量とノギスで測定した外寸から求めた体積より、成形体の密度（ｇ／ｍＬ）を算出した。なお、成形体の密度は、配合比から換算して成形体１ｍＬ中の炭素多孔体の質量（ｇ）として求めた。つまり、密度とは、吸着剤成形体における炭素多孔体の充填密度を指す。 Next, the obtained adsorbent molded body was dried at 80° C., and the outer dimensions after drying were measured with a caliper. The density (g/mL) of the molded product was calculated from the dry weight after drying and the volume obtained from the outer dimensions measured with a caliper. The density of the molded body was calculated as the mass (g) of the carbon porous material in 1 mL of the molded body by converting from the blending ratio. That is, the density refers to the packing density of the carbon porous body in the adsorbent molded body.
次いで、吸着材成形体の特性を以下の方法で求めた。結果を下記表２に示す。
（１）アンモニア吸着量差ΔＡＮＨ３の算出
温度２７３Ｋにてアンモニアを吸着材成形体に吸着させた。飽和蒸気圧Ｐ０は、４３０ｋＰａであった。圧力Ｐを変化させた際に吸着材成形体１ｇに吸着するアンモニアの吸着量［ｇ／ｇ］を測定し、圧力Ｐ［ｋＰａ］を横軸とし、吸着材成形体１ｇに吸着したアンモニア吸着量［ｇ／ｇ］を縦軸として吸着等温線を作成した。この吸着等温線より、アンモニア圧力が３９０ｋＰａのときのアンモニア吸着量Ａ３９ＮＨ３、及びアンモニア圧力が３００ｋＰａのときのアンモニア吸着量Ａ３０ＮＨ３を読み取り、Ａ３９ＮＨ３からＡ３０ＮＨ３を減じてアンモニア吸着量差ΔＡＮＨ３（＝アンモニア吸着量Ａ３９ＮＨ３−アンモニア吸着量Ａ３０ＮＨ３）を求めた。
Next, the characteristics of the adsorbent molded body were determined by the following methods. The results are shown in Table 2 below.
(1) Calculation of ammonia adsorption amount difference ΔA NH3 Ammonia was adsorbed on the adsorbent compact at a temperature of 273K. The saturated vapor pressure P 0 was 430 kPa. The adsorption amount [g/g] of ammonia adsorbed on the adsorbent compact 1g when the pressure P was changed was measured, and the pressure P [kPa] was taken as the horizontal axis, and the ammonia adsorption amount adsorbed on the adsorbent compact 1g was measured. An adsorption isotherm was created with [g/g] as the vertical axis. From this adsorption isotherm, the ammonia adsorption amount when ammonia pressure of 390kPa A 39NH3, and ammonia pressure reading ammonia adsorption amount A 30NH3 when the 300 kPa, ammonia adsorption amount difference by subtracting the A 30NH3 from A 39NH3 ΔA NH3 ( =Ammonia adsorption amount A 39NH3 -Ammonia adsorption amount A 30NH3 ) was determined.
（２）窒素吸着量差ΔＡＮ２の算出
温度７７Ｋにて窒素ガスを吸着材成形体に吸着させた。相対圧力Ｐ／Ｐ０を変化させた際に吸着材成形体１ｇに吸着する窒素の吸着量［ｃｍ３（ＳＴＰ）／ｇ］を測定し、相対圧力Ｐ／Ｐ０を横軸とし、吸着材成形体１ｇに吸着した窒素吸着量［ｃｍ３（ＳＴＰ）／ｇ］を縦軸として吸着等温線を作成した。この吸着等温線より、相対圧力Ｐ／Ｐ０が０．５のときの窒素吸着量Ａ０．５Ｎ２、及び相対圧力Ｐ／Ｐ０が０．８５のときのＡ０．８５Ｎ２を読み取り、Ａ０．５Ｎ２からＡ０．８５Ｎ２を減じて窒素吸着量の差ΔＡＮ２（＝窒素吸着量Ａ０．５Ｎ２−窒素吸着量Ａ０．８５Ｎ２）を求めた。
(2) Calculation of nitrogen adsorption amount difference ΔA N2 Nitrogen gas was adsorbed on the adsorbent compact at a temperature of 77K. When the relative pressure P/P 0 was changed, the adsorption amount [cm 3 (STP)/g] of nitrogen adsorbed on the adsorbent compact 1 g was measured, and the relative pressure P/P 0 was taken as the horizontal axis. An adsorption isotherm was created with the nitrogen adsorption amount [cm 3 (STP)/g] adsorbed on 1 g of the molded body as the vertical axis. From this adsorption isotherm, the nitrogen adsorption amount A 0.5N2, and relative pressure P / P 0 at a relative pressure P / P 0 of 0.5 reads the A 0.85N2 when the 0.85, A 0 difference in the nitrogen adsorption amount by subtracting the a 0.85N2 from .5N2 ΔA N2 (= nitrogen adsorption a 0.5N2 - nitrogen adsorption a 0.85N2) was determined.
なお、得られたアンモニア吸着量差ΔＡＮＨ３及び窒素吸着量差ΔＡＮ２を用い、横軸をΔＡＮ２［ｇ／ｇ］とし、縦軸をΔＡＮＨ３［ｇ／ｇ］としてプロットすると、図２の関係が得られた。 Using the obtained ammonia adsorption amount difference ΔA NH3 and nitrogen adsorption amount difference ΔA N2 , plotting the horizontal axis as ΔA N2 [g/g] and the vertical axis as ΔA NH3 [g/g], A relationship was obtained.
（比較例１）
実施例１において、炭素多孔体を市販の活性炭（商品名：メソコール、（株）キャタラー製）に代えるとともに、ヒドロキシプロピルメチルセルロースの量を１１部から７部に変更し、水の量を４００部から１６０部に変更したこと以外は、実施例１と同様にして、吸着材成形体を作製し、成形体の密度等の算出を行なった。結果を下記表２に示す。
なお、市販の活性炭の特性を実施例１と同様の方法で求め、結果を表１に示す。
(Comparative Example 1)
In Example 1, the carbon porous material was replaced with commercially available activated carbon (trade name: Mesocol, manufactured by Cataler Co., Ltd.), the amount of hydroxypropylmethyl cellulose was changed from 11 parts to 7 parts, and the amount of water was changed from 400 parts. An adsorbent shaped article was prepared in the same manner as in Example 1 except that the amount was changed to 160 parts, and the density and the like of the shaped article were calculated. The results are shown in Table 2 below.
The characteristics of commercially available activated carbon were determined by the same method as in Example 1, and the results are shown in Table 1.
表２に示すように、実施例１では、活性炭を用いた比較例１に比べて、窒素吸着量について約８倍の吸着量差が現れた。また、アンモニアガスを用いた場合も同様に、実施例１では、比較例１に比べて、アンモニア吸着量について約９倍の吸着量差が現れた。
また、成形体１ｍＬ当たりでの窒素吸着量差は、実施例１が０．１６３であり、比較例１（０．０４３）の約４倍の吸着量差が現れた。
As shown in Table 2, in Example 1, as compared with Comparative Example 1 in which activated carbon was used, the difference in the adsorption amount of nitrogen was about 8 times. Similarly, in the case where ammonia gas was used, in Example 1, a difference in the adsorption amount of ammonia was about 9 times that in Comparative Example 1.
Further, the difference in the amount of adsorbed nitrogen per 1 mL of the molded body was 0.163 in Example 1, and a difference in the amount of adsorbed nitrogen that was about four times that in Comparative Example 1 (0.043) appeared.
以上のように、本発明の吸着材成形体は、従来の活性炭を用いた吸着材料に比べ、相対圧力の比較的大きい領域において、相対圧力の変化量に対する窒素吸着量の変化量が大きいといえる。したがって、実施例１の吸着材成形体は、窒素及びアンモニア等の気体の圧力を変化させた場合の気体の吸脱着速度及び吸脱着量を向上させることができる。
これに対して、従来の活性炭を用いた吸着材料では、窒素及びアンモニア等の気体の圧力を変化させても、気体の吸脱着速度及び吸脱着量を実施例１と同様に高めることができない。
As described above, it can be said that the adsorbent shaped body of the present invention has a large change amount of the nitrogen adsorption amount with respect to the change amount of the relative pressure in a region where the relative pressure is relatively large, as compared to the conventional adsorbent material using activated carbon. .. Therefore, the adsorbent shaped article of Example 1 can improve the adsorption/desorption rate and adsorption/desorption amount of gas when the pressure of gas such as nitrogen and ammonia is changed.
On the other hand, with the conventional adsorbent material using activated carbon, even if the pressure of gas such as nitrogen and ammonia is changed, the adsorption/desorption rate and adsorption/desorption amount of gas cannot be increased as in Example 1.
また、図２は、窒素吸着量差△ＡＮ２とアンモニア吸着量差△ＡＮＨ３との関係を示しており、△ＡＮ２及び△ＡＮＨ３の両者間には一定の相関関係があることがわかる。 Further, FIG. 2 shows the relationship between the nitrogen adsorption amount difference ΔA N2 and the ammonia adsorption amount difference ΔA NH3, and it can be seen that there is a certain correlation between both ΔA N2 and ΔA NH3. ..
本発明の吸着材成形体は、例えば、窒素やアンモニアの吸着材として利用可能であり、更には、電気化学キャパシタの電極材料、熱交換型反応器の吸着材、バイオ燃料電池の電極に酵素を担持する材料、キャニスタの吸着材、又は燃料精製設備の吸着材などへの利用が可能である。 The adsorbent molded article of the present invention can be used as, for example, an adsorbent for nitrogen or ammonia, and further, an electrode material for an electrochemical capacitor, an adsorbent for a heat exchange reactor, an enzyme for a biofuel cell electrode. It can be used as a material to be carried, an adsorbent for a canister, or an adsorbent for a fuel refining facility.
Claims (1)
ＩＵＰＡＣで定義されるＩＶ型に分類される窒素吸着等温線における、温度７７ケルビンでの飽和蒸気圧Ｐ０に対する平衡圧力Ｐの相対圧力Ｐ／Ｐ０が０．５及び０．８５であるときのそれぞれの窒素吸着量の差の絶対値が０．１５ｇ／ｍＬ以上であり、
前記炭素多孔体は、前記窒素吸着等温線のαｓプロット解析から算出したミクロ細孔容量が、０．１ｍＬ／ｇ以下であり、
前記炭素多孔体は、ＩＵＰＡＣで定義されるＩＶ型に分類される窒素吸着等温線において、温度７７Ｋでの飽和蒸気圧Ｐ ０ に対する平衡圧力Ｐの相対圧力Ｐ／Ｐ ０ が０．５のときの窒素吸着量が５００ｃｍ ３ （ＳＴＰ）／ｇ以下であり、かつ、前記相対圧力Ｐ／Ｐ ０ が０．８５のときの窒素吸着量が６００ｃｍ ３ （ＳＴＰ）／ｇ以上１１００ｃｍ ３ （ＳＴＰ）／ｇ以下であり、
前記炭素多孔体は、ＢＥＴ法による比表面積が１０００ｍ ２ ／ｇ以上である吸着材成形体。 At least powdery carbon porous material , containing hydroxypropylmethyl cellulose or trimethyl cellulose ,
When the relative pressure P/P 0 of the equilibrium pressure P to the saturated vapor pressure P 0 at a temperature of 77 Kelvin is 0.5 and 0.85 in the nitrogen adsorption isotherm classified into type IV defined by IUPAC. The absolute value of the difference in each nitrogen adsorption amount is 0.15 g/mL or more,
The carbon porous body, micropore volume calculated from αs plot analysis of the nitrogen adsorption isotherm state, and are less 0.1 mL / g,
In the nitrogen adsorption isotherm classified into IV type defined by IUPAC, the carbon porous material has a relative pressure P/P 0 of the equilibrium pressure P to the saturated vapor pressure P 0 at a temperature of 77 K of 0.5. When the nitrogen adsorption amount is 500 cm 3 (STP)/g or less and the relative pressure P/P 0 is 0.85, the nitrogen adsorption amount is 600 cm 3 (STP)/g or more and 1100 cm 3 (STP)/g. Is less than
The carbon porous body, the adsorbent shaped body BET specific surface area is Ru der 1000 m 2 / g or more.
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