JP6483477B2 - Method for producing calcium salt and method for producing porous carbon - Google Patents
Method for producing calcium salt and method for producing porous carbon Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 38
- 229910052799 carbon Inorganic materials 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- 159000000007 calcium salts Chemical class 0.000 title claims description 31
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 89
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 43
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 15
- 239000000920 calcium hydroxide Substances 0.000 claims description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 15
- AAEHPKIXIIACPQ-UHFFFAOYSA-L calcium;terephthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 AAEHPKIXIIACPQ-UHFFFAOYSA-L 0.000 claims description 15
- -1 cation hydroxide Chemical class 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000011575 calcium Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Description
本発明は、カルシウム塩の製造方法及び炭素多孔体の製造方法に関する。 The present invention relates to a method for producing a calcium salt and a method for producing a carbon porous body.
従来、炭素多孔体としては、例えば、炭素骨格の一部が窒素原子で置換されたものが提案されている（特許文献１）。この炭素多孔体は、平均細孔径が２ｎｍ以下のミクロ細孔構造を有している。また、セルサイズが約０．１μｍの低密度の炭素発泡体も提案されている（特許文献２）。この炭素発泡体は、レゾルシノールとホルムアルデヒドとの重縮合によって得られるポリマークラスタを共有結合的に架橋してゲルを合成し、そのゲルを超臨界条件で処理してエアロゲルとし、そのエアロゲルを炭素化することによって合成されている。 Conventionally, as a carbon porous body, for example, a carbon skeleton in which a part of the carbon skeleton is substituted with a nitrogen atom has been proposed (Patent Document 1). This carbon porous body has a micropore structure with an average pore diameter of 2 nm or less. A low-density carbon foam having a cell size of about 0.1 μm has also been proposed (Patent Document 2). In this carbon foam, a polymer cluster obtained by polycondensation of resorcinol and formaldehyde is covalently crosslinked to synthesize a gel, and the gel is treated under supercritical conditions to form an airgel, and the airgel is carbonized. Is synthesized.
ところで、メソ細孔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差に対する窒素吸着量差が大きい炭素多孔体は知られておらず、当然、こうした炭素多孔体を容易に製造する方法も知られていなかった。このような炭素多孔体は、特定ガスの脱着材への利用のほか、電気化学キャパシタの電極材料やバイオ燃料電池の酵素電極を担持する材料、キャニスタの吸着材、燃料精製設備の吸着材などへの利用が期待される。 By the way, there is no known carbon porous body that has a mesopore structure, but has a large difference in nitrogen adsorption amount relative to the relative pressure difference in a relatively large region of relative pressure. Of course, there is a method for easily manufacturing such a carbon porous body. It was not known. Such carbon porous materials can be used not only as desorbing materials for specific gases, but also as electrode materials for electrochemical capacitors, materials supporting enzyme electrodes for biofuel cells, canister adsorbents, and adsorbents for fuel purification equipment. Is expected to be used.
このような多孔体の炭素材料の原料として芳香族化合物、特に、芳香族カルボン酸化合物のカルシウム塩を用いる場合がある。このとき、芳香族カルボン酸とカルシウム化合物とを反応させて芳香族カルボン酸化合物のカルシウム塩を作製するが、芳香族カルボン酸やカルシウム化合物は、溶媒への溶解度が低いことなどがあり、未反応の芳香族カルボン酸が残存するなど、例えば、収率を高めてカルシウム塩を得ることが困難であった。 An aromatic compound, particularly a calcium salt of an aromatic carboxylic acid compound may be used as a raw material for such a porous carbon material. At this time, the aromatic carboxylic acid and the calcium compound are reacted to produce a calcium salt of the aromatic carboxylic acid compound. However, the aromatic carboxylic acid or the calcium compound has low solubility in a solvent, and is not reacted. For example, it was difficult to obtain a calcium salt by increasing the yield.
本発明は、このような課題に鑑みなされたものであり、テレフタル酸のカルシウム塩をより効率よく得ることができるカルシウム塩の製造方法を提供することを主目的とする。また、効率よく得られたカルシウム塩を用いて炭素多孔体を得る炭素多孔体の製造方法を提供することを主目的とする。 This invention is made | formed in view of such a subject, and it aims at providing the manufacturing method of the calcium salt which can obtain the calcium salt of a terephthalic acid more efficiently. Moreover, it aims at providing the manufacturing method of the carbon porous body which obtains a carbon porous body using the calcium salt obtained efficiently.
上述した目的を達成するために鋭意研究したところ、本発明者らは、一価のカチオンの水酸化物と水とを少量添加して混合すると、テレフタル酸のカルシウム塩をより効率よく得ることができることを見いだし、本発明を完成するに至った。 As a result of diligent research to achieve the above-mentioned object, the present inventors can obtain a calcium salt of terephthalic acid more efficiently when a small amount of monovalent cation hydroxide and water are added and mixed. The inventors have found what can be done and have completed the present invention.
即ち、本発明のカルシウム塩の製造方法は、
テレフタル酸と水酸化カルシウムと一価カチオンの水酸化物とを混合してテレフタル酸カルシウムを生成する生成工程、を含むものである。
That is, the method for producing the calcium salt of the present invention comprises:
A production step of producing calcium terephthalate by mixing terephthalic acid, calcium hydroxide, and a hydroxide of a monovalent cation.
また、本発明の炭素多孔体の製造方法は、
上述のカルシウム塩の製造方法で生成したテレフタル酸カルシウムを不活性雰囲気中、５５０℃以上７００℃以下で加熱することで炭素／炭酸カルシウム複合体を形成し、形成した炭素／炭酸カルシウム複合体から炭酸カルシウムを溶解除去し、炭素多孔体を得る処理工程、を含むものである。
In addition, the method for producing a porous carbon body of the present invention includes:
A carbon / calcium carbonate complex is formed by heating calcium terephthalate produced by the above-described method for producing a calcium salt in an inert atmosphere at 550 ° C. or more and 700 ° C. or less, and carbon dioxide is formed from the formed carbon / calcium carbonate complex. A treatment step of dissolving and removing calcium to obtain a carbon porous body.
本発明のカルシウム塩の製造方法では、テレフタル酸のカルシウム塩をより効率よく得ることができる。この理由は、以下のように推測される。例えば、テレフタル酸および水酸化カルシウムは水への溶解度が低いため、そのまま反応させると、テレフタル酸のカルシウム塩の生成が不充分となることがある。本発明では、少量の一価カチオンの水酸化物（水酸化リチウムなど）を添加することにより、まず、テレフタル酸の一価カチオン塩が生成し、テレフタル酸の水中への溶解度が大きく向上する。この溶解したテレフタル酸塩と水酸化カルシウムとが、カチオン交換することによりテレフタル酸カルシウムとなり、全てのテレフタル酸がカルシウム塩となるものと推察される。 In the method for producing a calcium salt of the present invention, a calcium salt of terephthalic acid can be obtained more efficiently. The reason is presumed as follows. For example, since terephthalic acid and calcium hydroxide have low solubility in water, if they are reacted as they are, the formation of calcium salt of terephthalic acid may be insufficient. In the present invention, by adding a small amount of monovalent cation hydroxide (such as lithium hydroxide), first, a monovalent cation salt of terephthalic acid is generated, and the solubility of terephthalic acid in water is greatly improved. The dissolved terephthalate and calcium hydroxide are presumed to be calcium terephthalate by cation exchange, and all terephthalic acid becomes calcium salt.
本発明のカルシウム塩の製造方法は、テレフタル酸と水酸化カルシウムと一価カチオンの水酸化物（以下、単に水酸化物ともいう）とを混合してテレフタル酸カルシウムを生成する生成工程、を含むものである。この工程においては、まず、テレフタル酸が一価カチオンと反応し、テレフタル酸の一価カチオンの塩が生成する。次に、このテレフタル酸塩が水酸化カルシウムのカルシウムと置換し、テレフタル酸カルシウムが生成するものと考えられる。テレフタル酸は、溶媒（例えば水）への溶解度が比較的低いが、一価カチオンの塩となることにより、溶解度が高まり、水酸化カルシウムとの反応性がより高まると考えられる。 The method for producing a calcium salt of the present invention includes a production step of producing calcium terephthalate by mixing terephthalic acid, calcium hydroxide and a monovalent cation hydroxide (hereinafter also simply referred to as hydroxide). It is a waste. In this step, first, terephthalic acid reacts with a monovalent cation to produce a salt of a monovalent cation of terephthalic acid. Next, it is considered that this terephthalate is substituted for calcium hydroxide to produce calcium terephthalate. Although terephthalic acid has a relatively low solubility in a solvent (for example, water), it is considered that by becoming a salt of a monovalent cation, the solubility is increased and the reactivity with calcium hydroxide is further increased.
生成工程では、テレフタル酸のモル数Ｔに対する水酸化物のモル数Ｈであるモル比Ｈ／Ｔが０．０１以上０．０５以下の範囲とすることが好ましい。この範囲では、テレフタル酸の一価カチオン塩からテレフタル酸カルシウムへの置換反応をより円滑に進めることができる。このモル比Ｈ／Ｔは、０．０１以上０．０３以下の範囲とすることがより好ましい。また、テレフタル酸のモル数Ｔに対する水酸化カルシウムのモル数Ｃであるモル比Ｃ／Ｔが１以上１．２以下の範囲とすることが好ましい。 In the production step, the molar ratio H / T, which is the mole number H of the hydroxide with respect to the mole number T of terephthalic acid, is preferably in the range of 0.01 to 0.05. In this range, the substitution reaction from the monovalent cation salt of terephthalic acid to calcium terephthalate can be promoted more smoothly. The molar ratio H / T is more preferably in the range of 0.01 to 0.03. The molar ratio C / T, which is the number C of calcium hydroxide to the number T of terephthalic acid, is preferably in the range of 1 to 1.2.
生成工程では、水酸化物のモル濃度が０．０１５ｍｏｌ／Ｌ以上０．０７ｍｏｌ／Ｌ以下の範囲となるよう水を加えてテレフタル酸と水酸化カルシウムと水酸化物とを混合することが好ましい。このモル濃度の範囲では、テレフタル酸カルシウムの収率をより高めることができる。なお、上記モル比Ｈ／Ｔが０．０１未満では、水酸化物の添加量が極めて少ないため、テレフタル酸の溶解が進みにくく、良好なカルシウム塩を得にくい。一方、モル比Ｈ／Ｔが０．０５を超えると、このモル濃度の範囲での水の添加量は極めて少ないのでテレフタル酸と水酸化カルシウムと水酸化物との混合が均一に進みにくくなる。この水酸化物のモル濃度は、０．０３ｍｏｌ／Ｌ以上０．０５ｍｏｌ／Ｌ以下の範囲であることがより好ましく０．０４ｍｏｌ／Ｌとすることが更に好ましい。この生成工程では、固相反応により進行してテレフタル酸カルシウムを生成するものとしてもよい。即ち、この生成工程は、微量の水の存在下で行うものとしてもよい。 In the production step, it is preferable to add terephthalic acid, calcium hydroxide, and hydroxide so that water has a molar concentration of 0.015 mol / L to 0.07 mol / L. In this molar concentration range, the yield of calcium terephthalate can be further increased. When the molar ratio H / T is less than 0.01, the amount of hydroxide added is very small, so that the dissolution of terephthalic acid is difficult to proceed and it is difficult to obtain a good calcium salt. On the other hand, if the molar ratio H / T exceeds 0.05, the amount of water added in this molar concentration range is extremely small, so that mixing of terephthalic acid, calcium hydroxide, and hydroxide does not proceed uniformly. The molar concentration of the hydroxide is more preferably in the range of 0.03 mol / L to 0.05 mol / L, and still more preferably 0.04 mol / L. In this production step, calcium terephthalate may be produced by proceeding by a solid phase reaction. That is, this generation step may be performed in the presence of a small amount of water.
生成工程では、一価カチオンの水酸化物であれば特に限定されないが、水酸化物として水酸化リチウム、水酸化ナトリウム、水酸化カリウム及び水酸化アンモニウムのうち１以上を用いることが好ましい。このうち、水酸化リチウムを用いることがより好ましい。例えば、ナトリウムやカリウムは、炭素の賦活剤として機能してしまうことがあるが、水酸化リチウムは、その後の炭素多孔体を作製する際に、影響を与えにくく、好ましい。 Although it will not specifically limit if it is a hydroxide of a monovalent cation in a production | generation process, It is preferable to use 1 or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonium hydroxide as a hydroxide. Among these, it is more preferable to use lithium hydroxide. For example, sodium or potassium may function as a carbon activator, but lithium hydroxide is preferred because it hardly affects the subsequent carbon porous body.
生成工程において、混合するときの温度は、１００℃以下、より好ましくは６０℃以下、更に好ましくは４０℃以下の範囲で行うことができ、室温としてもよい。水酸化物を添加することにより、テレフタル酸の反応性が高まるため、より低い温度でテレフタル酸カルシウムを生成することができる。混合時間は、テレフタル酸の量にもよるが、例えば、６時間以上、７２時間以下の範囲とすることが好ましい。 In the production step, the mixing temperature may be 100 ° C. or lower, more preferably 60 ° C. or lower, and still more preferably 40 ° C. or lower, and may be room temperature. By adding a hydroxide, the reactivity of terephthalic acid increases, so that calcium terephthalate can be produced at a lower temperature. The mixing time depends on the amount of terephthalic acid, but is preferably in the range of 6 hours to 72 hours, for example.
本発明の炭素多孔体の製造方法は、上述したカルシウム塩の製造方法で生成したテレフタル酸カルシウムを不活性雰囲気中、５５０℃以上７００℃以下で加熱することで炭素／炭酸カルシウム複合体を形成し、形成した炭素／炭酸カルシウム複合体から炭酸カルシウムを溶解除去し、炭素多孔体を得る処理工程、を含むものである。 The method for producing a porous carbon body of the present invention forms a carbon / calcium carbonate composite by heating calcium terephthalate produced by the above-described calcium salt production method in an inert atmosphere at 550 ° C. or more and 700 ° C. or less. And a treatment step of dissolving and removing calcium carbonate from the formed carbon / calcium carbonate composite to obtain a porous carbon body.
処理工程において、不活性雰囲気としては、窒素雰囲気やアルゴン雰囲気などが挙げられる。加熱温度については、５５０℃〜７００℃の範囲では、良好な多孔体が得られるため、好ましい。加熱後に得られる炭素／炭酸カルシウム複合体は、層状炭化物の層間に炭酸カルシウムが入り込んだ構造をとっていると推察される。加熱温度での保持時間は、例えば５０時間以下としてもよい。このうち、０．５〜２０時間が好ましく、１〜１０時間がより好ましい。０．５時間以上では、炭素と炭酸カルシウムとの複合体の形成が十分に行われる。２０時間以下では、ＢＥＴ比表面積の比較的大きな炭素多孔体が得られる。 In the treatment process, examples of the inert atmosphere include a nitrogen atmosphere and an argon atmosphere. The heating temperature is preferably in the range of 550 ° C. to 700 ° C. because a good porous body can be obtained. The carbon / calcium carbonate composite obtained after heating is presumed to have a structure in which calcium carbonate enters between layers of layered carbides. The holding time at the heating temperature may be, for example, 50 hours or less. Among these, 0.5 to 20 hours are preferable, and 1 to 10 hours are more preferable. In 0.5 hour or more, the formation of a complex of carbon and calcium carbonate is sufficiently performed. In 20 hours or less, a carbon porous body having a relatively large BET specific surface area can be obtained.
処理工程において、炭酸カルシウムを溶解除去する方法としては、炭素／炭酸カルシウム複合体を液体で洗浄することが挙げられる。洗浄液としては、例えば、水や酸性水溶液を用いることが好ましい。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。この洗浄を行うことにより、複合体中の炭酸カルシウムが存在していた箇所は空洞（気孔）になると推察される。 In the treatment step, the method for dissolving and removing calcium carbonate includes washing the carbon / calcium carbonate complex with a liquid. As the cleaning liquid, for example, water or an acidic aqueous solution is preferably used. Examples of the acidic aqueous solution include aqueous solutions of hydrochloric acid, nitric acid, acetic acid, and the like. By performing this cleaning, it is presumed that the place where calcium carbonate in the composite was present becomes a cavity (pore).
得られた炭素多孔体は、吸着材として利用することができる。吸着する物質は、例えば、アンモニアなどが挙げられる。この吸着材は、アンモニア圧力が３９０ｋＰａのときのアンモニア吸着量からアンモニア圧力が３００ｋＰａのときのアンモニア吸着量を差し引いた値が０．５０ｇ／ｇ以上であることが好ましい。こうすれば、アンモニア圧力を調節することにより、多量のアンモニアを吸着させたりそれを放出させたりすることができる。 The obtained carbon porous material can be used as an adsorbent. Examples of the adsorbing substance include ammonia. The adsorbent preferably has a value obtained by subtracting the ammonia adsorption amount when the ammonia pressure is 300 kPa from the ammonia adsorption amount when the ammonia pressure is 390 kPa to 0.50 g / g or more. By so doing, a large amount of ammonia can be adsorbed or released by adjusting the ammonia pressure.
以上詳述した本実施形態のカルシウム塩の製造方法では、テレフタル酸のカルシウム塩をより効率よく得ることができる。この理由は、以下のように推測される。例えば、テレフタル酸および水酸化カルシウムは水への溶解度が低いため、そのまま反応させると、テレフタル酸のカルシウム塩の生成が不充分となることがある。本発明では、少量の水酸化物（水酸化リチウムなど）を添加することにより、まず、テレフタル酸の一価カチオン塩が生成し、テレフタル酸の水中への溶解度が大きく向上する。この溶解したテレフタル酸塩と水酸化カルシウムとが、カチオン交換することでテレフタル酸カルシウムとなり、全てのテレフタル酸がカルシウム塩となるものと推察される。また、モル比Ｈ／Ｔが０．０１以上０．０５以下の範囲で水酸化物を添加するため、テレフタル酸の一部が一価カチオン塩になるなど、徐々に反応が進むため、テレフタル酸カルシウムへの反応をより促進することができる。 The calcium salt of terephthalic acid can be obtained more efficiently in the method for producing a calcium salt of the present embodiment described in detail above. The reason is presumed as follows. For example, since terephthalic acid and calcium hydroxide have low solubility in water, if they are reacted as they are, the formation of calcium salt of terephthalic acid may be insufficient. In the present invention, by adding a small amount of hydroxide (such as lithium hydroxide), first, a monovalent cation salt of terephthalic acid is generated, and the solubility of terephthalic acid in water is greatly improved. This dissolved terephthalate and calcium hydroxide are presumed to be calcium terephthalate by cation exchange, and all terephthalic acid becomes calcium salt. In addition, since the hydroxide is added in a molar ratio H / T of 0.01 or more and 0.05 or less, a part of the terephthalic acid becomes a monovalent cation salt. The reaction to calcium can be further promoted.
なお、本発明は上述した実施形態に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.
以下には、本発明のカルシウム塩及び炭素多孔体を具体的に製造した例を実験例として説明する。なお、実験例１〜９、１１が本発明の実施例に相当し、実験例１０が比較例に相当する。 Below, the example which manufactured the calcium salt and carbon porous body of this invention concretely is demonstrated as an experiment example. Experimental examples 1 to 9 and 11 correspond to examples of the present invention, and experimental example 10 corresponds to a comparative example.
［実験例１］
テレフタル酸（以下ＰＴＡ）０．１ｍｏｌと、水酸化カルシウム（Ｃａ（ＯＨ）2：水酸化Ｃａ）０．１ｍｏｌとを粉末混合した。混合比はモル比でＰＴＡ：水酸化Ｃａ＝１：１とした。これに水酸化リチウム（ＬｉＯＨ）０．００１ｍｏｌを添加し、混合した。この組成比は、ＰＴＡ：水酸化Ｃａ：ＬｉＯＨ＝１：１：０．０１である。これに水をＬｉＯＨ濃度が０．０４ｍｏｌ／Ｌになるように添加し、混合して静置した。生成塩をＡｒ気流中で熱重量分析（ＴＧ測定）を行った。２００℃〜４００℃の区間における質量値から、質量減少率（質量％）を求めた。
[Experimental Example 1]
0.1 mol of terephthalic acid (hereinafter referred to as PTA) and 0.1 mol of calcium hydroxide (Ca (OH) 2 : Ca hydroxide) were mixed by powder. The mixing ratio was PTA: hydroxide Ca = 1: 1 in molar ratio. To this, 0.001 mol of lithium hydroxide (LiOH) was added and mixed. This composition ratio is PTA: hydroxide Ca: LiOH = 1: 1: 0.01. Water was added thereto so that the LiOH concentration was 0.04 mol / L, mixed and allowed to stand. The generated salt was subjected to thermogravimetric analysis (TG measurement) in an Ar stream. The mass reduction rate (mass%) was determined from the mass value in the section of 200 ° C. to 400 ° C.
［実験例２〜６］
ＰＴＡ：水酸化Ｃａ：ＬｉＯＨのモル比をそれぞれ１：１：０．０２、１：１：０．０３とした以外は、実験例１と同様に作製したものを実験例２，３とした。また、ＰＴＡ：水酸化Ｃａ：ＬｉＯＨのモル比を１：１．２：０．０１とした以外は、実験例１と同様に作製したものを実験例４とした。また、ＰＴＡ：水酸化Ｃａ：ＬｉＯＨのモル比を１：１：０．０１とし、ＬｉＯＨのモル濃度をそれぞれ０．０１ｍｏｌ／Ｌ、０．０８ｍｏｌ／Ｌとした以外は、実験例１と同様に作製したものを実験例５、６とした。
[Experimental Examples 2 to 6]
Experimental examples 2 and 3 were prepared in the same manner as in Experimental Example 1 except that the molar ratio of PTA: hydroxide Ca: LiOH was 1: 1: 0.02 and 1: 1: 0.03, respectively. Further, Experimental Example 4 was prepared in the same manner as in Experimental Example 1 except that the molar ratio of PTA: hydroxide Ca: LiOH was set to 1: 1.2: 0.01. Moreover, it was the same as that of Experimental Example 1 except that the molar ratio of PTA: hydroxide Ca: LiOH was 1: 1: 0.01 and the molar concentration of LiOH was 0.01 mol / L and 0.08 mol / L, respectively. The produced samples were designated as Experimental Examples 5 and 6.
［実験例７〜９］
ＰＴＡ：水酸化Ｃａ：ＭＯＨ（Ｍ＝１価のカチオン）のモル比を１：１：０．０２とし、ＭＯＨをそれぞれＮａＯＨ、ＫＯＨ、ＮＨ4ＯＨとした以外は、実験例１と同様に作製したものを実験例７〜９とした。
[Experimental Examples 7 to 9]
Prepared in the same manner as in Experimental Example 1 except that the molar ratio of PTA: hydroxide Ca: MOH (M = 1 cation) was 1: 1: 0.02, and MOH was NaOH, KOH, and NH 4 OH, respectively. These were made into Experimental Examples 7-9.
［実験例１０］
ＰＴＡ０．１ｍｏｌと、水酸化Ｃａ０．１ｍｏｌとを、水１００ｍｌ中に分散させ、８０℃の水浴で４時間加熱することで、テレフタル酸Ｃａ塩の結晶を生成させた。結晶を濾過で分取して、室温で風乾し、得られたものを実験例１０とした。
[Experimental Example 10]
Crystals of terephthalic acid Ca salt were produced by dispersing 0.1 mol of PTA and 0.1 mol of Ca hydroxide in 100 ml of water and heating in an 80 ° C. water bath for 4 hours. The crystals were collected by filtration and air-dried at room temperature.
（結果と考察）
図１は、実験例１、１０の質量減少測定結果である。図２は、水を加えたＬｉＯＨのモル濃度（ｍｏｌ／Ｌ）に対するＴＧの質量減少率（質量％）の関係図である。図１に示すように、室温〜１５０℃の低温領域において、質量減少が見られた。これは、結晶水の脱離によるものと推察された。また、２００℃〜４００℃の高温領域において質量減少が見られた。これは、未反応のテレフタル酸が昇華することによるものと推察された。したがって、この高温領域の質量減少が少ないものが、良好にＣａ塩となっていると評価することができる。また、実験例１〜１０におけるこの高温領域での質量減少の測定結果を表１に示す。実験例１０では、質量減少が１２．３質量％と大きく、未反応のテレフタル酸が比較的多く残っていると推察された。一方、ＰＴＡの１ｍｏｌに対しＬｉＯＨが０．０１〜０．０３ｍｏｌの範囲で含む実験例１〜４では、特に質量減少率が５質量％以下と少なく、未反応の原料成分（ＰＴＡ）をより減少することができることがわかった。なお、ＰＴＡの１ｍｏｌに対しＣａのモル数が１〜１．２ｍｏｌでも同じであった（実験例４）。また、ＬｉＯＨのモル濃度は、図２に示すように、０．０１５〜０．０７ｍｏｌ／Ｌの範囲において質量減少率が５質量％以下と少なく、未反応の原料成分（ＰＴＡ）をより減少することができることがわかった。また、ＭＯＨのＭをＮａ，Ｋ，ＮＨ4とした実験例７〜９においても、質量減少率がより小さく、未反応の原料成分（ＰＴＡ）をより減少することができることがわかった。
(Results and discussion)
FIG. 1 shows measurement results of mass loss in Experimental Examples 1 and 10. FIG. 2 is a relationship diagram of the mass decrease rate (mass%) of TG with respect to the molar concentration of LiOH (mol / L) with water added. As shown in FIG. 1, mass reduction was observed in a low temperature range from room temperature to 150 ° C. This was presumed to be due to desorption of crystal water. Moreover, the mass reduction | decrease was seen in the 200 degreeC-400 degreeC high temperature area | region. This was presumed to be due to sublimation of unreacted terephthalic acid. Therefore, it can be evaluated that the low mass loss in the high temperature region is a good Ca salt. In addition, Table 1 shows the measurement results of mass reduction in this high temperature region in Experimental Examples 1 to 10. In Experimental Example 10, the mass reduction was as large as 12.3% by mass, and it was assumed that a relatively large amount of unreacted terephthalic acid remained. On the other hand, in Experimental Examples 1 to 4 in which LiOH is contained in the range of 0.01 to 0.03 mol with respect to 1 mol of PTA, the mass reduction rate is particularly small at 5% by mass or less and the unreacted raw material component (PTA) is further reduced. I found out that I can do it. In addition, it was the same even if the mol number of Ca was 1-1.2 mol with respect to 1 mol of PTA (Experimental Example 4). In addition, as shown in FIG. 2, the molar concentration of LiOH is as low as 5% by mass or less in the range of 0.015 to 0.07 mol / L, and the unreacted raw material component (PTA) is further reduced. I found out that I could do it. Moreover, also in Experimental Examples 7 to 9 in which M of MOH was Na, K, NH 4 , it was found that the mass reduction rate was smaller and the unreacted raw material component (PTA) could be further reduced.
（炭素多孔体の作製）
テレフタル酸のカルシウム塩（４ｇ）を電気管状炉内に配置し、その管状炉内を不活性ガス（流速０．１Ｌ／分）でフロー置換した。不活性ガスとしては窒素ガスを用いたが、アルゴンガスを用いてもよい。ガスフローを維持したまま、管状炉温度を設定温度まで１時間かけて昇温した。ここでは、設定温度を５５０℃にした。昇温完了後、ガスフローを維持したまま、その設定温度で２時間保持し、その後室温まで冷却した。これにより、管状炉内には、炭素と炭酸カルシウムとの複合体が生成した。複合体を管状炉から取り出し、水５００ｍＬに分散させた。分散液に２ｍｏｌ／Ｌの塩酸を５０ｍＬ添加し、撹拌した。すると、炭酸カルシウムの分解により発泡が見られた。分散液をろ過後、乾燥して得られた炭素多孔体を実験例１１とした（収量約１ｇ）。
(Production of porous carbon)
A calcium salt of terephthalic acid (4 g) was placed in an electric tube furnace, and the inside of the tube furnace was flow-replaced with an inert gas (flow rate 0.1 L / min). Nitrogen gas is used as the inert gas, but argon gas may be used. While maintaining the gas flow, the tubular furnace temperature was raised to the set temperature over 1 hour. Here, the set temperature was set to 550 ° C. After completion of the temperature increase, the gas flow was maintained and maintained at the set temperature for 2 hours, and then cooled to room temperature. Thereby, the composite_body | complex of carbon and calcium carbonate produced | generated in the tubular furnace. The composite was removed from the tubular furnace and dispersed in 500 mL of water. 50 mL of 2 mol / L hydrochloric acid was added to the dispersion and stirred. Then, foaming was observed due to decomposition of calcium carbonate. The carbon porous body obtained by filtering and drying the dispersion was used as Experimental Example 11 (yield: about 1 g).
（炭素多孔体の特性値測定）
実験例１１の炭素多孔体について、液体窒素温度（７７Ｋ）における窒素吸着測定を行い、比表面積を求めた。図３は、実験例１１の７７Ｋでの窒素吸着等温線である。ＢＥＴ比表面積は、ＢＥＴ解析から算出した。実験例１１の炭素多孔体は、ＢＥＴ比表面積が１３８９ｍ2／ｇであった。また、図３に示す実験例１１の炭素多孔体の窒素吸着等温線は、ＩＵＰＡＣ分類のＩＶ型（メソ細孔を持つことを示す型）に属するものであった。したがって、実験例１１の炭素多孔体は、ほぼメソ細孔から構成されていると推察された。
(Characteristic value measurement of carbon porous material)
The carbon porous body of Experimental Example 11 was subjected to nitrogen adsorption measurement at a liquid nitrogen temperature (77K) to obtain a specific surface area. FIG. 3 is a nitrogen adsorption isotherm at 77K of Experimental Example 11. The BET specific surface area was calculated from BET analysis. The porous carbon body of Experimental Example 11 had a BET specific surface area of 1389 m 2 / g. Further, the nitrogen adsorption isotherm of the carbon porous material of Experimental Example 11 shown in FIG. 3 belongs to the IUPAC classification IV type (a type indicating mesopores). Therefore, it was guessed that the carbon porous body of Experimental Example 11 was substantially composed of mesopores.
なお、本発明は上述した実施例に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 In addition, this invention is not limited to the Example mentioned above at all, and as long as it belongs to the technical scope of this invention, it cannot be overemphasized that it can implement with a various aspect.
本発明は、炭素材料の原料製造に関する技術分野に利用可能である。 The present invention can be used in the technical field related to the raw material production of carbon materials.
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