JP2020055713A - Method for producing silver carbonate - Google Patents
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- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 title claims abstract description 54
- 229910001958 silver carbonate Inorganic materials 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 72
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 33
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- -1 silver ions Chemical class 0.000 claims abstract description 17
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005273 aeration Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 34
- 239000002244 precipitate Substances 0.000 description 24
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 11
- 238000001237 Raman spectrum Methods 0.000 description 9
- 229910001923 silver oxide Inorganic materials 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 229910001414 potassium ion Inorganic materials 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
本発明は、炭酸銀製造方法に関するものである。 The present invention relates to a method for producing silver carbonate.
銀は、貴金属としての価値を有する他、工業製品の材料としての利用価値も非常に高い金属である。銀イオンと陰イオンとが化合してなる銀塩も、抗菌性等を有することから利用価値が高い。水に不溶性の銀塩は、ろ別により容易に回収することができることから、資源として有用な銀を廃液等から回収するプロセスにおいて中間生成物として重要な化合物である。 Silver is a metal having a value as a precious metal and a very high value as a material for industrial products. Silver salts formed by combining silver ions and anions are also highly useful because they have antibacterial properties and the like. A water-insoluble silver salt is an important compound as an intermediate product in a process of recovering silver, which is useful as a resource, from a waste liquid or the like since it can be easily recovered by filtration.
特に、水に不溶性の銀塩の一つである炭酸銀は、加熱により容易に炭酸を除去して銀を回収することができ、そのときに発生するガスが低毒性である。炭酸銀は、そのままでも利用価値が高いだけでなく、触媒としての利用も可能である。また、炭酸銀は、容易に分解可能な有機酸銀の原料として用いられ、機能性材料の原料としても用いられる。 In particular, silver carbonate, which is one of water-insoluble silver salts, can easily remove carbonic acid by heating to recover silver, and the gas generated at that time has low toxicity. Silver carbonate has not only high utility value as it is, but also can be used as a catalyst. Further, silver carbonate is used as a raw material for easily decomposable organic acid silver and also as a raw material for functional materials.
従来の炭酸銀製造方法は、例えば、水に可溶性の銀塩である硝酸銀（ＡｇＮＯ３）の水溶液に、炭酸アンモニウム（（ＮＨ４）２ＣＯ３）または炭酸ナトリウム（Ｎａ２ＣＯ３）を添加する。そして、硝酸銀に由来する銀イオン（Ａｇ＋）と、炭酸アンモニウムまたは炭酸ナトリウムに由来する炭酸イオン（ＣＯ３ 2-）とを化合させることで、炭酸銀（Ａｇ２ＣＯ３）を製造する。 In a conventional silver carbonate production method, for example, ammonium carbonate ((NH 4 ) 2 CO 3 ) or sodium carbonate (Na 2 CO 3 ) is added to an aqueous solution of silver nitrate (AgNO 3 ), which is a silver salt soluble in water. . Then, the silver ions from silver nitrate (Ag +), that is compounds and carbonate ions (CO 3 2-) derived from ammonium carbonate or sodium carbonate, to produce silver carbonate (Ag 2 CO 3).
特許文献１には、炭酸銀を酸化銀に化学変化させる発明が開示されている。この文献に開示された発明は、炭酸銀を製造することを意図するものではない。この文献には、大気中の二酸化炭素または水溶液中に溶存している二酸化炭素が銀と反応することで、意図せず炭酸銀が製造されてしまう場合があることが記載されている。 Patent Document 1 discloses an invention in which silver carbonate is chemically changed into silver oxide. The invention disclosed in this document is not intended to produce silver carbonate. This document describes that silver carbonate may be produced unintentionally when carbon dioxide in the atmosphere or carbon dioxide dissolved in an aqueous solution reacts with silver.
大気中の二酸化炭素を用いて炭酸銀を製造できる場合があることが特許文献１に示唆されていると言える。このような炭酸銀製造方法は、カーボンニュートラルであるので、環境負荷の点で好ましい。しかし、特許文献１には、酸化銀より炭酸銀を効率よく製造する為の条件については何ら記載がない。 It can be said that Patent Document 1 suggests that silver carbonate can be produced using carbon dioxide in the atmosphere. Since such a method for producing silver carbonate is carbon neutral, it is preferable from the viewpoint of environmental load. However, Patent Document 1 does not disclose any conditions for efficiently producing silver carbonate from silver oxide.
本発明は、上記問題点を解消する為になされたものであり、大気中の二酸化炭素を利用して炭酸銀を効率よく製造することができる方法を提供することを目的とする。 The present invention has been made to solve the above problems, and has as its object to provide a method capable of efficiently producing silver carbonate using carbon dioxide in the atmosphere.
本発明の炭酸銀製造方法は、(1) 水に可溶性の銀塩と１価の金属の水酸化物とを混合して、銀塩に由来する銀イオンに対する金属のイオンのモル比が４.４４倍以上である水溶液を作製する混合ステップと、(2) 化学平衡反応により、水溶液に二酸化炭素を溶解させ、その溶解した二酸化炭素から炭酸イオンを生成させ、水溶液に含まれる銀イオンと炭酸イオンとを化合させて炭酸銀を析出させる析出ステップと、を備える。 According to the method for producing silver carbonate of the present invention, (1) a silver salt soluble in water and a hydroxide of a monovalent metal are mixed, and the molar ratio of the metal ion to silver ion derived from the silver salt is 4. (2) dissolving carbon dioxide in the aqueous solution by a chemical equilibrium reaction, generating carbonate ions from the dissolved carbon dioxide, and forming silver ions and carbonate ions contained in the aqueous solution. And depositing silver carbonate to form silver carbonate.
本発明の炭酸銀製造方法は、析出ステップにおいて、水溶液を攪拌するのが好適であり、水溶液に対し通気を行うのが好適であり、また、水溶液の蒸発を防止するのが好適である。 In the method for producing silver carbonate of the present invention, in the precipitation step, it is preferable that the aqueous solution is stirred, the aqueous solution is preferably aerated, and the evaporation of the aqueous solution is preferably prevented.
本発明によれば、大気中の二酸化炭素を利用して炭酸銀を効率よく製造することができる。この炭酸銀製造方法は、カーボンニュートラルであるので、環境負荷の点で好ましい。 According to the present invention, silver carbonate can be efficiently produced using carbon dioxide in the atmosphere. Since this silver carbonate production method is carbon neutral, it is preferable from the viewpoint of environmental load.
以下、添付図面を参照して、本発明を実施するための形態を詳細に説明する。なお、図面の説明において同一の要素には同一の符号を付し、重複する説明を省略する。本発明は、これらの例示に限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。 Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same elements will be denoted by the same reference symbols, without redundant description. The present invention is not limited to these examples, but is indicated by the appended claims, and is intended to include all modifications within the meaning and scope equivalent to the appended claims.
図１は、本実施形態の炭酸銀製造方法のフローチャートである。本実施形態の炭酸銀製造方法は、混合ステップＳ１および析出ステップＳ２を順に行うことで、炭酸銀を製造する。 FIG. 1 is a flowchart of the method for producing silver carbonate according to the present embodiment. The silver carbonate production method of the present embodiment produces silver carbonate by sequentially performing the mixing step S1 and the precipitation step S2.
混合ステップＳ１では、水に可溶性の銀塩と１価の金属の水酸化物とを混合して、銀塩に由来する銀イオンに対する１価の金属のイオンのモル比が４.４４倍以上である水溶液を作製する。水に可溶性の銀塩として、例えば、硝酸銀（ＡｇＮＯ３）および硫酸銀（Ａｇ２ＳＯ４）等が挙げられる。１価の金属の水酸化物として、例えば、水酸化カリウム（ＫＯＨ）、水酸化ナトリウム（ＮａＯＨ）、水酸化リチウム（ＬｉＯＨ）、水酸化セシウム（ＣｓＯＨ）および水酸化ルビジウム（ＲｂＯＨ）等が挙げられる。水溶液において銀塩に由来する銀イオンに対する１価の金属のイオンのモル比を４.４４倍以上とする理由については後述する。 In the mixing step S1, a water-soluble silver salt and a monovalent metal hydroxide are mixed, and the molar ratio of the monovalent metal ion to the silver ion derived from the silver salt is 4.44 times or more. Make an aqueous solution. Examples of the silver salt soluble in water include silver nitrate (AgNO 3 ) and silver sulfate (Ag 2 SO 4 ). Examples of the monovalent metal hydroxide include potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), cesium hydroxide (CsOH), and rubidium hydroxide (RbOH). . The reason why the molar ratio of the monovalent metal ion to the silver ion derived from the silver salt in the aqueous solution is 4.44 times or more will be described later.
析出ステップＳ２では、混合ステップＳ１で作製した水溶液に二酸化炭素を溶解させ、その溶解した二酸化炭素から炭酸イオンを生成させる。そして、水溶液に含まれる銀イオンと炭酸イオンとを化合させて炭酸銀を析出させる。水溶液に溶解させる二酸化炭素は、大気中に含まれるものであってよい。 In the precipitation step S2, carbon dioxide is dissolved in the aqueous solution prepared in the mixing step S1, and carbonate ions are generated from the dissolved carbon dioxide. Then, silver ions and carbonate ions contained in the aqueous solution are combined to precipitate silver carbonate. Carbon dioxide dissolved in the aqueous solution may be contained in the atmosphere.
下記（１）式で示される化学平衡反応により、大気中の二酸化炭素（ＣＯ２(g)）は水中に溶解する。さらに、下記（２）式で示される化学平衡反応により、その溶解した二酸化炭素（ＣＯ２(aq)）と水（Ｈ２Ｏ）とから炭酸（Ｈ２ＣＯ３）が生成される。大気中の二酸化炭素の濃度は約４００ｐｐｍであると言われている。たとえ精製された超純水等であっても、その水を大気中に静置すると、その水は或る濃度の炭酸を含むようになる。 The carbon dioxide (CO 2 (g)) in the atmosphere is dissolved in water by the chemical equilibrium reaction represented by the following formula (1). Further, carbon dioxide (H 2 CO 3 ) is generated from the dissolved carbon dioxide (CO 2 (aq)) and water (H 2 O) by a chemical equilibrium reaction represented by the following formula (2). It is said that the concentration of carbon dioxide in the atmosphere is about 400 ppm. Even if purified ultrapure water or the like is allowed to stand in the atmosphere, the water will contain a certain concentration of carbonic acid.
下記（３）式および（４）式で示される化学平衡反応により、水溶液のｐＨ値が大きくなると、水溶液中の炭酸（Ｈ２ＣＯ３）から水素イオン（Ｈ＋）が乖離して、炭酸水素イオン（ＨＣＯ３ −）および炭酸イオン（ＣＯ３ 2-）が生成される。この化学平衡反応における酸解離定数（ｐＫａ値）は、温度２５℃において６.３５および１０.５６である。これらの値を用いると、水溶液中での炭酸、炭酸水素イオンおよび炭酸イオンそれぞれの存在割合を計算することができる。 When the pH value of the aqueous solution increases due to the chemical equilibrium reaction represented by the following formulas (3) and (4), hydrogen ions (H + ) dissociate from carbonic acid (H 2 CO 3 ) in the aqueous solution and hydrogen carbonate Ions (HCO 3 − ) and carbonate ions (CO 3 2− ) are generated. The acid dissociation constants (pKa values) in this chemical equilibrium reaction are 6.35 and 10.56 at a temperature of 25 ° C. By using these values, it is possible to calculate the proportions of carbonic acid, bicarbonate ions and carbonate ions in the aqueous solution.
図２は、水溶液中での炭酸、炭酸水素イオンおよび炭酸イオンそれぞれの存在割合とｐＨ値との関係を示すグラフである。この図を見て分かるとおり、水溶液のｐＨ値が或る値より大きいアルカリ性の条件下では炭酸イオンの存在割合が大きい。すなわち、水溶液のｐＨ値を大きくすることで、大気中の二酸化炭素の溶解が進み、炭酸イオンの生成が進む。このように、水溶液をアルカリ性とするのみで、水溶液中の炭酸イオンの存在割合を大きくすることができる。 FIG. 2 is a graph showing the relationship between the respective proportions of carbonic acid, bicarbonate ion, and carbonate ion in the aqueous solution and the pH value. As can be seen from this figure, under alkaline conditions where the pH value of the aqueous solution is greater than a certain value, the proportion of carbonate ions present is large. That is, by increasing the pH value of the aqueous solution, the dissolution of carbon dioxide in the atmosphere proceeds, and the generation of carbonate ions proceeds. As described above, only by making the aqueous solution alkaline, the proportion of carbonate ions in the aqueous solution can be increased.
水溶液に含まれる銀塩に由来する銀イオンと炭酸イオンとを化合させて炭酸銀を析出させる。炭酸銀の溶解度積は、温度２０℃において８.５８×１０-12である。例えば、水溶液中の銀イオンの濃度が１ｍＭである場合に、共存可能な炭酸イオンの濃度は８.５８μＭであり、炭酸イオン濃度がこの値を超えると炭酸銀が析出する。 Silver ions derived from silver salts contained in the aqueous solution are combined with carbonate ions to precipitate silver carbonate. The solubility product of silver carbonate is 8.58 × 10 −12 at a temperature of 20 ° C. For example, when the concentration of silver ions in the aqueous solution is 1 mM, the concentration of coexistable carbonate ions is 8.58 μM, and when the carbonate ion concentration exceeds this value, silver carbonate precipitates.
それぞれの化学平衡において下記（５）式〜（９）式で表される平衡定数が定義される。ＰCO2は、大気中の二酸化炭素の分圧である。［ＣＯ２(aq)］は、水溶液中の二酸化炭素の濃度である。［Ｈ２ＣＯ３］は、水溶液中の炭酸（Ｈ２ＣＯ３）の濃度である。［Ｈ＋］は、水溶液中の水素イオン（Ｈ＋）の濃度である。［ＨＣＯ３ −］は、水溶液中の炭酸水素イオン（ＨＣＯ３ −）の濃度である。［ＣＯ３ 2-］は、水溶液中の炭酸イオン（ＣＯ３ 2-）の濃度である。［Ｈ＋］は、水溶液中の水素イオン（Ｈ＋）の濃度である。［ＯＨ−］は、水溶液中の水酸イオン（ＯＨ−）の濃度である。それぞれの濃度の単位はＭ（＝mol／Ｌ）である。ＫＨは、上記（１）式の平衡定数である。Ｋhydrは、上記（２）式の平衡定数である。Ｋa1は、上記（３）式の酸解離定数である。Ｋa2は、上記（４）式の酸解離定数である。ＫＷは、水（Ｈ２Ｏ）の自己解離定数である。 In each chemical equilibrium, equilibrium constants represented by the following equations (5) to (9) are defined. PC02 is the partial pressure of carbon dioxide in the atmosphere. [CO 2 (aq)] is the concentration of carbon dioxide in the aqueous solution. [H 2 CO 3 ] is the concentration of carbonic acid (H 2 CO 3 ) in the aqueous solution. [H + ] is the concentration of hydrogen ions (H + ) in the aqueous solution. [HCO 3 − ] is the concentration of hydrogen carbonate ion (HCO 3 − ) in the aqueous solution. [CO 3 2- ] is the concentration of carbonate ion (CO 3 2- ) in the aqueous solution. [H + ] is the concentration of hydrogen ions (H + ) in the aqueous solution. [OH − ] is the concentration of hydroxyl ion (OH − ) in the aqueous solution. The unit of each concentration is M (= mol / L). K H is the equilibrium constant of the above equation (1). K hydr is the equilibrium constant of the above equation (2). K a1 is the acid dissociation constant of the above formula (3). Ka2 is the acid dissociation constant of the above formula (4). K W is a self-dissociation constant of water (H 2 O).
１価の金属の水酸化物として水酸化カリウムを想定して、水溶液中のカリウムイオン（Ｋ＋）の濃度を［Ｋ＋］と表す。水素イオンの濃度［Ｈ＋］に関して上記（５）式〜（９）式を整理すると、下記（１０）式が得られる。なお、水酸化カリウム以外の他の１価の金属の水酸化物を想定した場合にも、同じ式が得られる。これらの式を用いると、水溶液中の水酸化カリウム濃度から、二酸化炭素溶解平衡時の水溶液中の水素イオン濃度を計算することができ、さらに、水溶液中の炭酸イオン濃度を計算することができる。 Assuming potassium hydroxide as the monovalent metal hydroxide, the concentration of potassium ion (K + ) in the aqueous solution is represented as [K + ]. By rearranging the above equations (5) to (9) with respect to the hydrogen ion concentration [H + ], the following equation (10) is obtained. In addition, the same formula is obtained when assuming a hydroxide of a monovalent metal other than potassium hydroxide. Using these equations, the hydrogen ion concentration in the aqueous solution at the time of dissolution equilibrium with carbon dioxide can be calculated from the potassium hydroxide concentration in the aqueous solution, and further, the carbonate ion concentration in the aqueous solution can be calculated.
図３は、二酸化炭素溶解平衡時の炭酸イオン濃度と水酸化カリウム濃度との関係を示すグラフである。図中の丸印は、上記の式から計算により得られたものである。これを見て分かるとおり、炭酸イオン濃度は水酸化カリウム濃度に対して比例関係にあると見做すことができる。炭酸イオン濃度［ＣＯ３ 2-］とカリウムイオン濃度［Ｋ＋］との間の関係を最小二乗法により線形近似すると、下記（１１）式で表すことができる。図には、この式で表される直線も示されている。 FIG. 3 is a graph showing the relationship between the concentration of carbonate ions and the concentration of potassium hydroxide during equilibrium of carbon dioxide dissolution. The circles in the figure are obtained by calculation from the above equation. As can be seen, the carbonate ion concentration can be considered to be proportional to the potassium hydroxide concentration. When the relationship between the carbonate ion concentration [CO 3 2- ] and the potassium ion concentration [K + ] is linearly approximated by the least square method, it can be expressed by the following equation (11). The figure also shows a straight line represented by this equation.
この直線の傾きは０.４５である。したがって、はじめに溶解した金属イオンの量の０.４５倍の量の炭酸イオンを溶解させることができ、この炭酸イオン量に応じた量の炭酸銀を得ることができる。炭酸銀（Ａｇ２ＣＯ３）は２：１の組成の塩であるので、銀塩に由来する銀イオンと金属水酸化物に由来する１価の金属イオンとのモル比は、０.４５：２（＝１：４.４４）以上であることが望ましい。すなわち、１価の金属イオンの量は銀イオン量に対してモル比で４.４４倍以上であることが望ましい。 The slope of this straight line is 0.45. Therefore, it is possible to dissolve 0.45 times the amount of carbonate ions that was initially dissolved, and to obtain silver carbonate in an amount corresponding to the amount of carbonate ions. Since silver carbonate (Ag 2 CO 3 ) is a salt having a 2: 1 composition, the molar ratio of silver ions derived from a silver salt to monovalent metal ions derived from a metal hydroxide is 0.45: 2 (= 1: 4.44) or more is desirable. That is, the amount of the monovalent metal ion is desirably 4.44 times or more as much as the molar amount of the silver ion.
次に実施例１について説明する。混合ステップＳ１では、等量の硝酸銀水溶液（１００ｍＭ）および水酸化カリウム水溶液（５００ｍＭ）を混合した水溶液を作製した。この水溶液において、カリウムイオン量は、銀イオン量に対してモル比で５倍である。析出ステップＳ２では、この水溶液を所定時間（１時間、２４時間）に亘り室温で静置して、この間に化学平衡反応により析出物を生成した。 Next, a first embodiment will be described. In the mixing step S1, an aqueous solution was prepared by mixing equal amounts of an aqueous solution of silver nitrate (100 mM) and an aqueous solution of potassium hydroxide (500 mM). In this aqueous solution, the amount of potassium ions is five times the molar amount of silver ions. In the precipitation step S2, the aqueous solution was allowed to stand at room temperature for a predetermined time (1 hour, 24 hours), during which a precipitate was formed by a chemical equilibrium reaction.
図４は、実施例１における１時間静置後の析出物の顕微鏡写真である。図５は、実施例１における２４時間静置後の析出物の顕微鏡写真である。それぞれの視野サイズは２４９μｍ×１６６μｍである。図６は、実施例１における２４時間静置後の析出物のＸ線回折パターンを示す図である。図６の横軸は回折角であり、縦軸は回折強度である。 FIG. 4 is a photomicrograph of a precipitate after standing for 1 hour in Example 1. FIG. 5 is a photomicrograph of a precipitate after standing for 24 hours in Example 1. Each field size is 249 μm × 166 μm. FIG. 6 is a diagram showing an X-ray diffraction pattern of a precipitate after standing for 24 hours in Example 1. The horizontal axis in FIG. 6 is the diffraction angle, and the vertical axis is the diffraction intensity.
１時間静置後では、図４に示されるとおり粉末状の析出物が得られた。２４時間静置御では、図５に示されるとおり結晶状の析出物が得られた。それぞれの析出物をＸ線回折により分析したところ、１時間静置後の析出物は主に酸化銀であり、２４時間静置後の析出物は主に炭酸銀であることが分かった。２４時間静置後の析出物のＸ線回折パターン（図６（ａ））は、データベース（Powder Diffraction File 26-0339）の炭酸銀のＸ線回折パターン（図６（ｂ））とよく一致している。 After standing for 1 hour, a powdery precipitate was obtained as shown in FIG. After standing for 24 hours, a crystalline precipitate was obtained as shown in FIG. When each precipitate was analyzed by X-ray diffraction, it was found that the precipitate after standing for 1 hour was mainly silver oxide, and the precipitate after standing for 24 hours was mainly silver carbonate. The X-ray diffraction pattern of the precipitate after standing for 24 hours (FIG. 6 (a)) is in good agreement with the X-ray diffraction pattern of silver carbonate (FIG. 6 (b)) in the database (Powder Diffraction File 26-0339). ing.
高濃度の可溶性銀塩水溶液にアルカリ性水溶液を加えると酸化銀が生成されることが知られている（特許文献１参照）。この実施例１は、化学平衡反応により二酸化炭素の溶解が進むことで酸化銀が炭酸銀に変化することを示している。 It is known that silver oxide is generated when an alkaline aqueous solution is added to a high-concentration soluble silver salt aqueous solution (see Patent Document 1). Example 1 shows that the dissolution of carbon dioxide proceeds by a chemical equilibrium reaction, whereby silver oxide changes to silver carbonate.
二酸化炭素のアルカリ性水溶液への溶解が平衡に達するには、８０ｍＬ程度の液量の場合に、静置した状態で百時間程度を要するとされている（非特許文献１参照）。実施例１でも、二酸化炭素の溶解が進行することで炭酸濃度が上昇し、この炭酸濃度上昇に伴って、溶液の混合当初には酸化銀であったものが、炭酸と反応して炭酸銀へと変化したものと考えられる。 It is said that it takes about 100 hours for the solution of carbon dioxide to dissolve in the alkaline aqueous solution to reach equilibrium in the case of a liquid volume of about 80 mL while standing still (Non-Patent Document 1). Also in Example 1, as the dissolution of carbon dioxide progresses, the carbonic acid concentration increases. With the increase in the carbonic acid concentration, silver oxide was initially mixed with the solution, but reacted with carbonic acid to form silver carbonate. It is thought that it changed.
次に実施例２について説明する。混合ステップＳ１では、スライドガラス等の基板上に１００μＬの硝酸銀水溶液（１００ｍＭ）を滴下し、この滴下スポットに対して更に１００μＬの水酸化カリウム水溶液（２５０ｍＭ、２５００ｍＭ）を滴下し、基板上にて混合して水溶液を作製した。この水溶液において、カリウムイオン量は、銀イオン量に対してモル比で２.５倍または２５倍である。析出ステップＳ２では、この水溶液を４８時間に亘り室温で静置して、この間に化学平衡反応により水溶液内に黄色の結晶状の析出物を生成した。また、析出ステップＳ２では、水溶液の蒸発を防止するために、湿度を高く保った状態で水溶液を静置した。 Next, a second embodiment will be described. In the mixing step S1, 100 μL of an aqueous solution of silver nitrate (100 mM) is dropped on a substrate such as a slide glass or the like, and a further 100 μL of an aqueous solution of potassium hydroxide (250 mM, 2500 mM) is dropped on the drop spot and mixed on the substrate. Thus, an aqueous solution was prepared. In this aqueous solution, the amount of potassium ions is 2.5 times or 25 times the molar amount of silver ions. In the precipitation step S2, the aqueous solution was allowed to stand at room temperature for 48 hours, during which a yellow crystalline precipitate was formed in the aqueous solution by a chemical equilibrium reaction. In addition, in the precipitation step S2, the aqueous solution was allowed to stand at a high humidity in order to prevent evaporation of the aqueous solution.
水溶液のｐＨ値が低下しても二酸化炭素の溶解が可能であることが知られている（非特許文献１参照）。この実施例２でも、水溶液のｐＨ値が低下しても４８時間経過後に二酸化炭素の溶解が十分に生じていることを確認できた。実施例２では、量が少ないことから、二酸化炭素の溶解飽和までの時間が短いと考えられる。 It is known that carbon dioxide can be dissolved even when the pH value of an aqueous solution is lowered (see Non-Patent Document 1). Also in Example 2, it was confirmed that the dissolution of carbon dioxide was sufficient after 48 hours even if the pH value of the aqueous solution was lowered. In Example 2, since the amount is small, it is considered that the time until the solution saturation of carbon dioxide is short.
４８時間静置後の水溶液中の析出物に対してラマン分光によりラマンスペクトルを測定した。図７は、実施例２におけるモル比が２.５倍である場合の析出物のラマンスペクトルを示す図である。図８は、実施例２におけるモル比が２５倍である場合の析出物のラマンスペクトルを示す図である。図９は、比較のために示すものであり、水酸化カリウムに替えて炭酸ナトリウムを添加した場合に得られた析出物のラマンスペクトルを示す図である。これらの図において、横軸はラマンシフト量であり、縦軸はラマン光強度である。 The Raman spectrum of the precipitate in the aqueous solution after standing for 48 hours was measured by Raman spectroscopy. FIG. 7 is a diagram showing a Raman spectrum of a precipitate in the case where the molar ratio in Example 2 is 2.5 times. FIG. 8 is a diagram illustrating a Raman spectrum of a precipitate in the case where the molar ratio in Example 2 is 25 times. FIG. 9 is for comparison and is a diagram showing a Raman spectrum of a precipitate obtained when sodium carbonate was added instead of potassium hydroxide. In these figures, the horizontal axis is the Raman shift amount, and the vertical axis is the Raman light intensity.
図７〜図９の何れのラマンスペクトルにおいても、ラマンシフト量７００ｃｍ-1、１０５０ｃｍ-1、１５５０ｃｍ-1それぞれの付近にピークが存在している。これらのピークは炭酸銀に帰属されるものである。 In any of the Raman spectra of FIGS. 7-9, the Raman shift 700 cm -1, 1050 cm -1, are present peak near 1550 cm -1, respectively. These peaks are attributed to silver carbonate.
図７のラマンスペクトルはラマンシフト量４３５ｃｍ-1にピークを有するが、このピークは図８および図９のスペクトルには認められない。このピークは酸化銀に帰属されるものである。これは、カリウムイオン量が銀イオン量に対してモル比で２.５倍である場合（図７）には、酸化銀から炭酸銀への十分な変化が起きておらず、炭酸銀を効率よく製造することができなかったことを示している。また、カリウムイオン量が銀イオン量に対してモル比で２５倍である場合（図８）には、酸化銀から炭酸銀への十分な変化が起きて、炭酸銀を効率よく製造することができたことを示している。このことは、Ｘ線回折によっても確認された。 The Raman spectrum in FIG. 7 has a peak at a Raman shift of 435 cm −1 , but this peak is not recognized in the spectra in FIGS. 8 and 9. This peak is attributed to silver oxide. This is because when the amount of potassium ions is 2.5 times the molar amount of silver ions (FIG. 7), no sufficient change from silver oxide to silver carbonate has occurred, and the efficiency of silver carbonate is reduced. This indicates that it could not be manufactured well. When the amount of potassium ions is 25 times the molar amount of silver ions (FIG. 8), a sufficient change from silver oxide to silver carbonate occurs, and silver carbonate can be efficiently produced. Indicates that it was possible. This was also confirmed by X-ray diffraction.
これまでに説明した実施例では、少量の炭酸銀を製造した。より多くの量の炭酸銀を製造するには、混合ステップＳ１において作製する水溶液の量を多くする必要がある。水溶液の量が多くなると、析出ステップＳ２において水溶液を静置して化学平衡反応により析出物を生成するのでは、炭酸銀の製造に長時間を要することになる。そこで、析出ステップＳ２において、化学平衡反応を促進させて時間を短縮するために、水溶液を攪拌するのが好適であり、また、水溶液に対し通気を行うのも好適である。 In the examples described so far, a small amount of silver carbonate was produced. In order to produce a larger amount of silver carbonate, it is necessary to increase the amount of the aqueous solution produced in the mixing step S1. When the amount of the aqueous solution increases, it takes a long time to produce silver carbonate if the aqueous solution is allowed to stand in the precipitation step S2 to generate a precipitate by a chemical equilibrium reaction. Therefore, in the deposition step S2, it is preferable to stir the aqueous solution in order to promote the chemical equilibrium reaction and shorten the time, and it is also preferable to vent the aqueous solution.
例えば、混合ステップＳ１において、４０ｍＬの硝酸銀水溶液（１ｍＭ）と４０ｍＬの水酸化カリウム水溶液（５ｍＭ）とを容器内で混合して水溶液を作製する。そして、析出ステップＳ２において、７２時間経過に亘って室温にて、この容器内の水溶液をミキサ等で攪拌するとともにポンプ等で通気を行い、化学平衡反応により水溶液内に黄色の結晶状の析出物を生成する。 For example, in the mixing step S1, 40 mL of an aqueous solution of silver nitrate (1 mM) and 40 mL of an aqueous solution of potassium hydroxide (5 mM) are mixed in a container to prepare an aqueous solution. Then, in the precipitation step S2, the aqueous solution in this container is stirred with a mixer or the like and ventilated with a pump or the like at room temperature for 72 hours, and a yellow crystalline precipitate is formed in the aqueous solution by a chemical equilibrium reaction. Generate
以上のとおり、本実施形態の炭酸銀製造方法は、外部から炭酸塩等を反応系へ導入することなく、大気中の二酸化炭素により生成される炭酸のみを利用して炭酸銀を製造することができる。この炭酸銀製造方法は、カーボンニュートラルであるので、環境負荷の点で好ましい。また、銀塩に由来する銀イオンに対する１価の金属のイオンのモル比が４.４４倍以上であることにより、効率よく炭酸銀を製造することができる。 As described above, the silver carbonate production method of the present embodiment can produce silver carbonate using only carbonic acid generated by carbon dioxide in the atmosphere without introducing a carbonate or the like from the outside into the reaction system. it can. Since this silver carbonate production method is carbon neutral, it is preferable from the viewpoint of environmental load. When the molar ratio of the monovalent metal ion to silver ion derived from the silver salt is 4.44 or more, silver carbonate can be efficiently produced.
Claims (4)
化学平衡反応により、前記水溶液に二酸化炭素を溶解させ、その溶解した二酸化炭素から炭酸イオンを生成させ、前記水溶液に含まれる前記銀イオンと前記炭酸イオンとを化合させて炭酸銀を析出させる析出ステップと、
を備える炭酸銀製造方法。 Mixing by mixing a water-soluble silver salt and a monovalent metal hydroxide to produce an aqueous solution in which the molar ratio of the metal ion to silver ion derived from the silver salt is 4.44 times or more. Steps and
A precipitation step of dissolving carbon dioxide in the aqueous solution by a chemical equilibrium reaction, generating carbonate ions from the dissolved carbon dioxide, and combining the silver ions and the carbonate ions contained in the aqueous solution to precipitate silver carbonate. When,
A method for producing silver carbonate, comprising:
請求項１に記載の炭酸銀製造方法。 Stirring the aqueous solution in the deposition step,
The method for producing silver carbonate according to claim 1.
請求項１または２に記載の炭酸銀製造方法。 Performing aeration on the aqueous solution in the deposition step,
The method for producing silver carbonate according to claim 1.
請求項１〜３の何れか１項に記載の炭酸銀製造方法。 Preventing the evaporation of the aqueous solution in the deposition step,
The method for producing silver carbonate according to claim 1.
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