JP3545678B2 - Oxygen gas absorbent, method for producing the same, and method for absorbing oxygen gas - Google Patents

Description

【００５６】
さらに図１０として、表１の粉末Ｘ線回折値の結果をグラフ化した比較図を示す。
【００５７】
〈熱分析（ＴＧ）〉
上記実施例１で得られた錯体を、サンプル量 2.0mg、昇温速度１℃/min、最高温度５００℃、アルゴンガス通気下の条件下に測定したときの熱天秤（ＴＧ）グラフを図１１に示す。図１１から、温度２５０℃以上で急激な重量減少が見られることがわかる。
【００５８】
〈実施例１の錯体のＬi 含有量〉
実施例１で得た錯体につき、外部機関（株式会社島津総合分析試験センター）に依頼してＬi 含有量を測定した。この錯体中のＬi 量は 0.063％であり、錯体中のＬi 量は不純物程度であると考えられる。分析方法は次の通りである。
【００５９】
（分析方法）試料１０mgを採取し、硝酸１mlおよび塩酸 0.5mlを加えて加熱溶解し、純水にて全量２５mlとした。これを２倍に希釈し、Ｌi のイオン化を抑制するためにＫを１０００ppm 添加し、濃度 0.2、 0.4、 0.8ppm により検量線を作成して、検量線法によりＬi の定量を行った。得られた測定溶液中の値(ppm) を試料中濃度（％）に換算した（使用機器は島津原子吸光分光光度計）。
【００６０】
〈実施例１の錯体の元素分析結果〉
実施例１で得た錯体につき、外部機関（石川島検査計測株式会社）に依頼して元素分析を行ったところ、次の表２の結果が得られた。ただし、測定は、炭素、水素、灰分について行っており、( ) 内は灰分値から算出したものである。
【００６１】
【表２】

【００６２】
先のＬｉの分析結果で、錯体中には 0.063％のＬｉしか含まれていなかったので、灰分は事実上酸化銅（ＣｕＯ）であると考えられ、その灰分44.8％中のＣｕ成分は44.8×63.546/(63.546+15.999) = 35.8 ％であると計算できる。よって、実施例１の錯体は、表１に付記したように、 Cu₃(C₉H₃O₆)・7.4H₂Oであることがわかる。検算すると、 Cu₃(C₉H₃O₆)・7.4H₂O = 531.066、このうちのCu成分 = 63.546 ×3/531.066 = 35.9 %、C 成分 = 9×12.011/531.066 = 20.4 % 、H 成分 = (3+ 7.4×2)×1.008/531.066 = 3.4 % となる。
【００６３】
〈実施例１の錯体の繰り返し酸素ガス吸収性〉
実施例１で得た錯体につき、第１回目の酸素ガス吸収量の測定後、真空下で２５０℃で２〜３時間加熱処理して再生することにより、再度酸素ガス吸収量を測定する操作を繰り返したところ、第４回目にあっても、酸素ガス吸収量は低下しなかった。
【００６４】
【発明の効果】
本発明によれば、有機−無機複合錯体からなり、かつ酸素ガスを選択的に吸収するが、窒素ガスはほとんど吸収しない錯体からなる酸素ガス吸収剤を提供することができる。また、その酸素ガス吸収剤の工業的な製造法、その酸素ガス吸収剤を用いた酸素ガスの吸収方法を提供することができる。
【図面の簡単な説明】
【図１】実施例１の錯体のガス吸着量の測定結果を示したグラフである。
【図２】実施例２の錯体のガス吸着量の測定結果を示したグラフである。
【図３】実施例３の錯体のガス吸着量の測定結果を示したグラフである。
【図４】比較例１の錯体のガス吸着量の測定結果を示したグラフである。
【図５】比較例２の錯体のガス吸着量の測定結果を示したグラフである。
【図６】参考例１のモレキュラーシーブスのガス吸着量の測定結果を示したグラフである。
【図７】参考例２のモレキュラーシービングカーボンの吸着等温線図である。
【図８】実施例１で得た錯体の粉末Ｘ線回折図である。
【図９】比較例１で得た錯体の粉末Ｘ線回折図であり、図８の実施例１の結果も併記してある。

【図１０】表１の粉末Ｘ線回折値の結果をグラフ化した比較図である。
【図１１】実施例１で得られた錯体の熱分析（ＴＧ）グラフである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an oxygen gas absorbent comprising an organic-inorganic composite complex, and more particularly to an oxygen gas absorbent comprising a complex which selectively absorbs oxygen gas but hardly absorbs nitrogen gas. The present invention also relates to an industrial method for producing such an oxygen gas absorbent and a method for absorbing oxygen gas using such an oxygen gas absorbent .
[0002]
[Prior art]
As an adsorbent for adsorbing nitrogen gas and oxygen gas, zeolite and activated carbon having molecular sieve are known. Zeolites adsorb more nitrogen gas than oxygen gas, and molecular sieve activated carbon can adsorb oxygen gas faster than nitrogen gas. These adsorbents are used in gas separation devices such as PSA by utilizing their properties.
[0003]
Several studies have been made on metal complexes of benzenetricarboxylic acid, including trimesic acid, relevant to the present invention. Hereinafter, a few documents related to the present invention are listed as related documents.
[0004]
<Reference 1>
A Polish chemical journal "POLISH JOURNAL OF CHEMISTRY (FORMERLY ROCZNIKI CHEMII), 60, 697 (1986)" (Reference 1) contains a paper entitled "Production and properties of copper (II) complex with benzenetricarboxylic acid". Is published. According to this article, hemimellitate, trimesate and trimellitate of copper (II) are obtained as hydrated salts with a metal to ligand ratio of 3: 2.
[0005]
In the experiment, a complex of copper (II) and hemimellitic acid, trimesic acid or trimellitic acid was prepared by adding an equivalent 0.1 M solution of cupric nitrate to a hot solution of ammonium tricarboxylate (pH 5 to 5.5). The precipitate formed is heated in the mother liquor to 333-343 K (60-70 ° C.) for 0.5 h, filtered, washed with distilled water to remove NH ₄ ⁺ ions and brought to constant weight at 303 K (30 ° C.) It is obtained by drying until.
[0006]
The infrared absorption spectrum and the powder X-ray diffraction pattern of the obtained complex are also shown. The complex is dehydrated by heating and decomposed directly to CuO or with the formation of a Cu ₂ O intermediate, depending on the heating rate.
[0007]
<References 2, 2 '>
"J. Am. Chem. Soc., 1996, 118, 9096-9101" (Reference 2) entitled "Construction of porous solid from hydrogen-bonded metal complex of 1,3,5-benzenetricarboxylic acid". A paper has been published. Here, an aqueous mixture of M (II) (M = Co, Ni, Zn) acetate hydrate and acid type 1,3,5-benzenetricarboxylic acid (BTC) was placed in a furnace and heated to 140 ° C. By reacting at lever temperature for 24 hours, a substance that is formulated as M ₃ (BTC) ₂ .12H ₂ O has been obtained, and its detailed analysis has been performed. The obtained metal complex adsorbs and desorbs water and ammonia.
[0008]
This document 2 (and related documents) is described in "Science and Industry, 71 (10), 434-448 (1997)" (Reference 2 '), "Molecular zeolite-synthesis of organic-inorganic hybrid zeolite-". There is also a mention in a commentary on the subject, which states on page 444 that this complex does not exchange with oxygen, nitrogen, carbon monoxide, etc., but can reversibly adsorb and desorb water, ammonia, etc. is there.
[0009]
[Problems to be solved by the invention]
There are three types of benzenetricarboxylic acids: hemimelitic acid, trimesic acid, and trimellitic acid. Now, when benzenetricarboxylic acid is represented by BTC and a divalent metal is represented by M, the complex of the above-mentioned Reference 1 and References 2 and 2 ′ is considered to be represented by “M ₃ (BTC) ₂ .mH ₂ O”. m is 1, 2, 3, 4, 5, 6, 12, or the like.
[0010]
<Regarding Document 1>
The above-mentioned literature 1 merely mentions the basic properties of the complex obtained therewith, but does not mention its use. Further, there is no description that the complex is a porous substance, and there is no description that the complex is applicable to gas adsorption.
[0011]
<Regarding Documents 2 and 2 '>
References 2 and 2 'mentioned above mention gas absorption and desorption as well as the basic properties of the metal complexes obtained therefrom. However, regarding the adsorption and desorption of the gas of the metal complex, it does not exchange with oxygen, nitrogen, carbon monoxide and the like, but only states that water and ammonia can be reversibly adsorbed and desorbed. is there. The complexes of Literatures 2 and 2 ′ have a metal component of Co, Ni or Zn, and are different in substance from the Cu-based complex intended in the present invention.
[0012]
<Object of the present invention>
The present invention, in this background under organic - an inorganic composite complex, and that selectively absorb oxygen gas, to provide an oxygen gas absorbent consisting of the nitrogen gas absorbs little complex, its oxygen to provide an industrial method for producing gas absorbent, and it is an object to provide a method of absorbing oxygen gas using the oxygen gas absorbent.
[0013]
[Means for Solving the Problems]
The oxygen gas absorbent of the present invention,
A complex synthesized from a copper ion and an alkali metal trimesate ,
-Trimesic acid residue: When C ₆ H ₃ (COO) ₃ is L,
[Cu ₃ (L)] _n
Having a structural formula with a basic unit of,
-In terms of gas absorption behavior, it is characterized by comprising a complex having a property of selectively absorbing oxygen gas .
[0014]
The production method of the oxygen gas absorbent of the present invention is to obtain a complex by reacting a copper ion and an alkali metal trimesinate in a solvent that dissolves both, and then heat-treating the complex ,
-Trimesic acid residue: When C ₆ H ₃ (COO) ₃ is L,
[Cu ₃ (L)] _n
Having a structural formula with a basic unit of,
In terms of gas absorption behavior, an oxygen gas absorbent comprising a complex having a property of selectively absorbing oxygen gas is obtained .
[0015]
The method for absorbing oxygen gas of the present invention,
A complex synthesized from a copper ion and an alkali metal trimesate,
-Trimesic acid residue: When C ₆ H ₃ (COO) ₃ is L,
[Cu ₃ (L)] _n
Having a structural formula with a basic unit of,
In terms of gas absorption behavior, the present invention is characterized in that a complex having a property of selectively absorbing oxygen gas is used to absorb oxygen gas.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0017]
The oxygen gas absorbent of the present invention comprises a complex synthesized from copper ions and an alkali metal trimesate.
[0018]
As the copper ion source, cupric salts such as cupric acetate, cupric nitrate, cupric chloride and cupric sulfate are preferably used, and among these, cupric acetate is particularly important and practical. It is a target. In some cases, cuprous salts can also be used.
[0019]
Examples of the alkali metal trimesic acid include lithium, sodium, potassium, rubidium, and cesium salts of trimesic acid (that is, 1,3,5-benzenetricarboxylic acid), that is, an alkali metal is M, a trimesic acid residue: When C ₆ H ₃ (COO) ₃ is L, a salt represented by M ₃ (L) is preferably used. In some cases, a derivative in which at least one of H at positions 2, 4, and 6 of the benzene ring of trimesic acid is substituted with an alkyl group, an alkoxy group, a halogen, or the like (that is, in the present invention, “ The term "trimesic acid" is used to include such derivatives.)
[0020]
By the way, when the ammonium salt of trimesic acid is used, the obtained complex absorbs both oxygen gas and nitrogen gas as in Comparative Example 2 described later, and is not suitable for the purpose of the oxygen gas absorbent of the present invention. .
[0021]
The reaction is carried out in a solvent that dissolves both the copper salt and the alkali metal trimesate. As the solvent, an organic solvent, water, an organic solvent-water mixed solvent, or the like is used as long as it does not form a stable complex with both metal salts as raw materials. Among them, organic solvents include alcohols (methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, neopentyl alcohol, etc.), ketones (diethyl ketone, methyl ethyl ketone, cyclohexanone, etc.), ethers (Diethyl ether, dibutyl ether, methyl butyl ether, furan, etc.), esters (ethyl acetate, butyl acetate, etc.), cellosolves, polyhydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylol) And the like, and two or more kinds may be used in combination. Among organic solvents, alcohols are particularly important.
[0022]
Among the above solvents, a mixed solvent of 1/9 to 9/1 by weight of an alcohol (particularly ethanol) and water is particularly suitable in consideration of solubility, boiling point, and the like.
[0023]
The amount of the solvent used is not particularly limited, but is used in a large excess with respect to the total amount of the raw material copper salt and trimesic acid alkali metal salt, for example, on a weight basis, between the copper salt and the trimesic acid alkali metal salt. It is preferable to use about 10 to 2000 times, especially about 30 to 1000 times of the total amount in view of easy control of the reaction.
[0024]
Regarding the molar ratio of copper ion (copper salt) to trimesic acid alkali metal salt, 0.1 to 10 mol of trimesic acid alkali metal salt is often used per 1 mol of copper ion.
[0025]
The reaction temperature is 30 to 300 ° C, preferably 40 to 200 ° C, particularly preferably 50 to 180 ° C in the case of normal pressure reaction. If the reaction temperature is too low, the reaction rate will be low, and if the reaction temperature is too high, the product may be decomposed. When the solvent is, for example, a mixed solvent of ethanol / water, the reaction is often performed under reflux conditions.
[0026]
Normal reaction pressure is sufficient, but pressurized conditions may be used. If the reaction is carried out under a pressurized condition, although it is disadvantageous in terms of equipment, a higher reaction temperature can be adopted or the reaction time can be shortened.
[0027]
The reaction time varies greatly depending on the reaction temperature, reaction pressure, and the like, and cannot be unconditionally determined, but is often selected from a range of about 1 hour to 10 days.
[0028]
After completion of the reaction, when the system is cooled, a complex as a product is obtained as a precipitate. Therefore, if necessary, the solvent is evaporated to dryness, and washing or recrystallization with water or an organic solvent is performed. Thereby, the target complex (porous complex) is obtained.
[0029]
The obtained complex is heat-treated. Thereby, the complex is activated and expresses specificity in absorption of oxygen gas. The heat treatment temperature at this time is preferably set in the range of 100 to 350 ° C. When the heat treatment temperature is too low, activation is insufficient, while when too high, the complex may be decomposed. A particularly preferred range is 200 to 300 ° C.
[0030]
The complex thus obtained has a structural formula having [Cu ₃ (L)] _n as a basic unit from elemental analysis, where L is trimesic acid residue: C ₆ H ₃ (COO) _3. The main plane spacing d of the complex in powder X-ray diffraction is substantially 5.61 ° when a lithium salt is used as the alkali metal trimesinate. Very slightly soluble in water.
[0031]
Since this complex is porous and absorbs oxygen gas well but hardly absorbs nitrogen gas, it is useful as an oxygen gas absorbent.
[0032]
In addition, the gas adsorption amount of zeolite (molecular sieves), which is a typical example of the adsorbent, is based on the difference in the affinity between the adsorbent and the gas, and the amount of adsorption of N ₂ gas (having a quadrupole moment). And the adsorption amount of O ₂ gas (having no quadrupole moment) is small. On the other hand, in the case of molecular sieving carbon (carbon molecular sieves, that is, activated carbon with molecular sieve), which is also a representative example of the adsorbent, the amount of adsorption after a long time is the same for both N ₂ gas and O ₂ gas. O ₂ gas (Van der Waals molecular diameter 2.94Å) is better than N ₂ gas (Van der Waals molecular diameter 3.11Å) because the diffusion rate (ie, adsorption rate) is different due to the difference in molecular diameter of the adsorbed gas. Also, the adsorption speed is high, and within a short time, the O ₂ gas is adsorbed earlier than the N ₂ gas.
[0033]
From these facts, it can be seen that the complex of the present invention has a different gas adsorption behavior from zeolite and a different gas adsorption behavior from molecular sieving carbon (molecular sieve activated carbon).
[0034]
【Example】
Next, the present invention will be further described with reference to examples.
[0035]
<Measuring method>
The specific surface area and pore distribution were measured at a liquid nitrogen temperature using AccuSorb 2100E manufactured by Micromeritics, and the specific surface area was calculated by the BET method. The adsorption amounts of oxygen gas and nitrogen gas were measured at a temperature of 30.0 ° C. using AccuSorb 2100E.
[0036]
Example 1
213.2 mg (1.015 mmol) of trimesic acid was placed in a 100 ml Erlenmeyer flask, dissolved in 40 ml of a mixed solvent of ethanol / water at a volume ratio of 50/50, and further added with 111.0 mg (1.502 mmol) of lithium carbonate and dissolved. The flask was heated to evaporate the solvent and evaporated to dryness, yielding 228.0 mg (1.000 mmol) of white lithium trimesate.
[0037]
100.6 mg (0.504 mmol) of cupric acetate monohydrate was placed in a 300 ml three-necked flask, and 60 ml of a mixed solvent of ethanol / water at a volume ratio of 50/50 was added and dissolved. To this was added 75.5 mg (0.331 mmol) of lithium trimesate obtained above, and the mixture was heated under reflux overnight. After cooling the next day, the precipitate was filtered and dried by blowing nitrogen gas to obtain 93.6 mg of a light blue complex.
[0038]
This precipitate was heat-treated under vacuum at 250 ° C. for 3 hours, and the specific surface area (BET method, using nitrogen gas) was 98 m ² / g as measured by a specific surface area meter. FIG. 1 shows an adsorption isotherm at a temperature of 30.0 ° C. As shown in FIG. 1, the amount of gas absorbed under atmospheric pressure (760 mmHg) was 7.4 ml / g for oxygen gas, but only 1.0 ml / g for nitrogen gas.
[0039]
Example 2
212.5 mg (1.011 mmol) of trimesic acid was placed in a 100 ml Erlenmeyer flask, dissolved in 30 ml of a mixed solvent of ethanol / water at a volume ratio of 50/50, and further dissolved by adding 168.8 mg (1.593 mmol) of sodium carbonate. The flask was heated to evaporate the solvent and evaporated to dryness, yielding 275.8 mg (0.999 mmol) of white sodium trimesinate.
[0040]
102.9 mg (0.515 mmol) of cupric acetate monohydrate was placed in a 300 ml three-necked flask, and dissolved by adding 40 ml of a 50/50 mixed solvent of ethanol / water by volume. To this was added a solution obtained by dissolving 93.1 mg (0.337 mmol) of sodium trimesinate obtained above in 20 ml of a mixed solvent of ethanol / water at a volume ratio of 50/50, and the mixture was heated under reflux overnight. The next day, the mixture was cooled, and the precipitate was filtered and dried by blowing nitrogen gas to obtain 89.5 mg of a light blue complex.
[0041]
The precipitate was heat-treated under vacuum at 250 ° C. for 3 hours and measured with a specific surface area meter. The specific surface area (BET method, using nitrogen gas) was 39 m ² / g. FIG. 2 shows an adsorption isotherm at a temperature of 30.0 ° C. As shown in FIG. 2, the amount of gas absorbed under atmospheric pressure (760 mmHg) was 4.8 ml / g for oxygen gas, but only 0.2 ml / g for nitrogen gas.
[0042]
Example 3
421.4 mg (2.005 mmol) of trimesic acid was placed in a 100 ml Erlenmeyer flask, dissolved in 40 ml of a 50/50 mixed solvent of ethanol / water, and 419.1 mg (3.032 mmol) of potassium carbonate was further added and dissolved. The flask was heated to evaporate the solvent to dryness, yielding 650.1 mg (2.004 mmol) of white potassium trimesate.
[0043]
105.3 mg (0.527 mmol) of cupric acetate monohydrate was placed in a 300 ml three-necked flask, and dissolved by adding 40 ml of a 50/50 mixed solvent of ethanol / water in volume ratio. A solution prepared by dissolving 112.6 mg (0.347 mmol) of the potassium trimesinate obtained above in 20 ml of a mixed solvent of ethanol / water at a volume ratio of 50/50 was added thereto, and the mixture was heated under reflux overnight. The next day, the mixture was cooled, and the precipitate was filtered and dried by blowing nitrogen gas to obtain 93.0 mg of a light blue complex.
[0044]
This precipitate was heat-treated under vacuum at 240 ° C. for 4 hours, and the specific surface area (BET method, using nitrogen gas) was 40 m ² / g as measured by a specific surface area meter. FIG. 3 shows an adsorption isotherm at a temperature of 30.0 ° C. As shown in FIG. 3, the amount of gas absorbed under atmospheric pressure (760 mmHg) was 3.7 ml / g for oxygen gas, but only 0.2 ml / g for nitrogen gas.
[0045]
Comparative Example 1
202.2 mg (1.013 mmol) of cupric acetate monohydrate was placed in a 300 ml three-necked flask, and dissolved by adding 100 ml of ethanol. A solution of 420.8 mg (2.002 mmol) of trimesic acid dissolved in 50 ml of ethanol was added thereto, and the mixture was heated under reflux for one week. After one week, the heating was stopped and the mixture was cooled, and the precipitate was filtered and dried by blowing nitrogen gas to obtain 156.3 mg (0.244 mmol) of a blue precipitate [Cu ₃ (L) ₂ .2H ₂ O] _n. Was. The yield was about 72% based on cupric acetate used as starting material.
[0046]
This precipitate was heat-treated at 120 ° C. for 1 hour under vacuum and measured with a specific surface area meter. The specific surface area (BET method, using nitrogen gas) was 398 m ² / g, and the peak of the pore distribution had a radius of 11 ° or less. Met. FIG. 4 shows an adsorption isotherm at a temperature of 30.0 ° C. As shown in FIG. 4, the amount of gas absorption under atmospheric pressure (760 mmHg) was 4.6 ml / g for oxygen gas and 4.6 ml / g for nitrogen gas.
[0047]
Comparative Example 2
215.0 mg (1.023 mmol) of trimesic acid was placed in a 100 ml eggplant-shaped flask, dissolved in 20 ml of a mixed solvent of ethanol / water at a volume ratio of 50/50, and ammonium carbonate was further added until the solvent became alkaline. The flask was placed on a rotary evaporator, the solvent was evaporated in a water bath at 50 ° C., and the solid was evaporated to dryness, whereby 264.3 mg (1.012 mmol) of white ammonium trimesinate was obtained.
[0048]
101.2 mg (0.507 mmol) of cupric acetate monohydrate was placed in a 300 ml three-necked flask, and 60 ml of a mixed solvent of ethanol / water at a volume ratio of 50/50 was added and dissolved. A solution prepared by dissolving 87.5 mg (0.335 mmol) of ammonium trimesinate obtained above in 20 ml of a mixed solvent of ethanol / water at a volume ratio of 50/50 was added thereto, and the mixture was heated under reflux overnight. After cooling the next day, the precipitate was filtered and dried by blowing nitrogen gas to obtain 91.7 mg of a light blue complex.
[0049]
This precipitate was heat-treated under vacuum at 240 ° C. for 3 hours, and the specific surface area (BET method, using nitrogen gas) was 13 m ² / g as measured by a specific surface area meter. Further, FIG. 5 shows an adsorption isotherm at a temperature of 30.0 ° C. As shown in FIG. 5, the gas absorption at atmospheric pressure (760 mmHg) was 3.1 ml / g for oxygen gas and 2.6 ml / g for nitrogen gas.
[0050]
Reference Example 1
FIG. 6 shows an adsorption isotherm of Molecular Sieves 5A (30/60 mesh, manufactured by Gascro Industry Co., Ltd.) at room temperature (25 ° C.). As shown in FIG. 6, the gas adsorption amounts at room temperature (25 ° C.) and atmospheric pressure (760 mmHg) were 2.5 ml / g for oxygen gas and 7.2 ml / g for nitrogen gas.

[0051]
Reference Example 2
FIG. 7 shows the adsorption isotherm of molecular sieving carbon (MSC, “Morchibon 3A” manufactured by Takeda Pharmaceutical Co., Ltd.) at room temperature (25 ° C.), which is a molecular sieve activated carbon. As shown in FIG. 7, the amount of adsorbed gas at room temperature (25 ° C.) and atmospheric pressure (760 mmHg) was 7.3 ml / g for oxygen gas and 7.3 ml / g for nitrogen gas.
[0052]
<Powder X-ray diffraction>
The complexes obtained in Example 1 and Comparative Example 1 were further subjected to powder X-ray diffraction. The results are shown in Table 1 and also in FIG. 8 (Example 1) and FIG. 9 (Comparative Example 1 and Example 1 are also shown).
[0053]
Table 1 also shows the powder X-ray diffraction values of the complex of Reference 1 mentioned in the section of the prior art. In Table 1, References 1 and 2 refer to the data with the largest peak among the data related to Reference 1 from the data recorded in X-RAY POWDER DATA FILE (published by THE AMERICAN SOCIETY FOR TESTING MATERIALS). It was taken out and transcribed.
[0054]
・ Reference 1
X-RAY POWDER DATA FILE Registration No. 39-1962
Cu ₃ (C ₉ H ₃ O ₆ ) ₂・ 3H ₂ O
Copper benzene-1,3,5-tricarboxylate trihydrate
REF: Pol. J. Chem., 60 697 (1986) Brzyska, W., Wolodkiewicz, W.
・ Reference 1-2
X-RAY POWDER DATA FILE Registration No. 39-1963
Cu ₃ (C ₉ H ₃ O ₆ ) ₂
Copper benzene-1,3,5-tricarboxylate
REF: Pol. J. Chem., 60 697 (1986) Brzyska, W., Wolodkiewicz, W.
[0055]
[Table 1]

[0056]
Further, FIG. 10 shows a comparative diagram in which the results of the powder X-ray diffraction values in Table 1 are graphed.
[0057]
<Thermal analysis (TG)>
FIG. 11 shows a thermobalance (TG) graph when the complex obtained in Example 1 was measured under the conditions of a sample amount of 2.0 mg, a heating rate of 1 ° C./min, a maximum temperature of 500 ° C., and argon gas ventilation. Shown in From FIG. 11, it can be seen that a sharp weight loss is observed at a temperature of 250 ° C. or higher.
[0058]
<Li content of the complex of Example 1>
The Li content of the complex obtained in Example 1 was measured by requesting an external organization (Shimadzu Comprehensive Analytical Testing Center). The amount of Li in this complex is 0.063%, and the amount of Li in the complex is considered to be of the order of impurities. The analysis method is as follows.
[0059]
(Analysis method) A 10 mg sample was collected, dissolved by heating with 1 ml of nitric acid and 0.5 ml of hydrochloric acid, and adjusted to a total volume of 25 ml with pure water. This was diluted twice, and 1000 ppm of K was added to suppress the ionization of Li. A calibration curve was prepared based on the concentrations of 0.2, 0.4, and 0.8 ppm, and Li was quantified by the calibration curve method. The value (ppm) in the obtained measurement solution was converted to the concentration (%) in the sample (the equipment used was a Shimadzu atomic absorption spectrophotometer).
[0060]
<Elemental analysis results of complex of Example 1>
The complex obtained in Example 1 was subjected to elemental analysis by an external organization (Ishikawajima Inspection and Measurement Co., Ltd.), and the results in Table 2 below were obtained. However, the measurement was performed for carbon, hydrogen, and ash, and the values in parentheses are calculated from the ash value.
[0061]
[Table 2]

[0062]
As a result of the above analysis of Li, since only 0.063% of Li was contained in the complex, the ash was considered to be actually copper oxide (CuO), and the Cu component in the ash of 44.8% was 44.8 × It can be calculated that 63.546 / (63.546 + 15.999) = 35.8%. Therefore, as shown in Table 1, the complex of Example 1 is Cu ₃ (C ₉ H ₃ O ₆ ) · 7.4H ₂ O. When calculated, Cu ₃ (C ₉ H ₃ O ₆ ) ・ 7.4H ₂ O = 531.066, of which Cu component = 63.546 × 3 / 531.066 = 35.9%, C component = 9 × 12.011 / 531.066 = 20.4%, H component = (3 + 7.4 × 2) × 1.008 / 531.066 = 3.4%.
[0063]
<Repeated oxygen gas absorption of the complex of Example 1>
For the complex obtained in Example 1, after the first measurement of the amount of oxygen gas absorbed, a heat treatment was performed at 250 ° C. for 2 to 3 hours under vacuum to regenerate the complex. When it was repeated, the amount of oxygen gas absorbed did not decrease even at the fourth time.
[0064]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the oxygen gas absorbent which consists of a complex which consists of an organic-inorganic composite complex and absorbs oxygen gas selectively, but hardly absorbs nitrogen gas can be provided. Further , it is possible to provide an industrial production method of the oxygen gas absorbent and a method of absorbing oxygen gas using the oxygen gas absorbent .
[Brief description of the drawings]
FIG. 1 is a graph showing the measurement results of the gas adsorption amount of the complex of Example 1.
FIG. 2 is a graph showing a measurement result of a gas adsorption amount of the complex of Example 2.
FIG. 3 is a graph showing a measurement result of a gas adsorption amount of the complex of Example 3.
FIG. 4 is a graph showing a measurement result of a gas adsorption amount of the complex of Comparative Example 1.
FIG. 5 is a graph showing a measurement result of a gas adsorption amount of the complex of Comparative Example 2.
FIG. 6 is a graph showing the measurement results of the gas adsorption amount of the molecular sieve of Reference Example 1.
FIG. 7 is an adsorption isotherm of the molecular sieving carbon of Reference Example 2.
FIG. 8 is a powder X-ray diffraction chart of the complex obtained in Example 1.
FIG. 9 is a powder X-ray diffraction diagram of the complex obtained in Comparative Example 1, and also shows the result of Example 1 in FIG.

FIG. 10 is a comparative diagram in which the results of powder X-ray diffraction values in Table 1 are graphed.
FIG. 11 is a thermal analysis (TG) graph of the complex obtained in Example 1.

Claims (4)

A complex synthesized from a copper ion and an alkali metal trimesate ,
-Trimesic acid residue: When C ₆ H ₃ (COO) ₃ is L,
[Cu ₃ (L)] _n
Having a structural formula with a basic unit of,
In terms of gas absorption behavior, an oxygen gas absorbent comprising a complex having a property of selectively absorbing oxygen gas. A complex is obtained by reacting a copper ion and an alkali metal trimesate in a solvent in which both are dissolved, and then the complex is subjected to heat treatment ,
-Trimesic acid residue: When C ₆ H ₃ (COO) ₃ is L,
[Cu ₃ (L)] _n
Having a structural formula with a basic unit of,
In terms of gas absorption behavior, a method for producing an oxygen gas absorbent comprising obtaining an oxygen gas absorbent comprising a complex having a property of selectively absorbing oxygen gas. The method according to claim 2 , wherein the heat treatment temperature is 100 to 350C. A complex synthesized from a copper ion and an alkali metal trimesate,
・ Trimesic acid residue: C ₆ H _Three (COO) _Three Is L
 [Cu _Three (L)] _n
Having a structural formula with a basic unit of,
In terms of gas absorption behavior, an oxygen gas absorption method characterized by absorbing oxygen gas using a complex having a property of selectively absorbing oxygen gas.

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