JPH048373B2 - - Google Patents
Info
- Publication number
- JPH048373B2 JPH048373B2 JP59128438A JP12843884A JPH048373B2 JP H048373 B2 JPH048373 B2 JP H048373B2 JP 59128438 A JP59128438 A JP 59128438A JP 12843884 A JP12843884 A JP 12843884A JP H048373 B2 JPH048373 B2 JP H048373B2
- Authority
- JP
- Japan
- Prior art keywords
- potassium
- aqueous solution
- sodium
- antimony
- potassium chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000007864 aqueous solution Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 32
- 229910001415 sodium ion Inorganic materials 0.000 claims description 27
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 claims description 24
- 229910052787 antimony Inorganic materials 0.000 claims description 22
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 22
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 64
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 61
- 239000001103 potassium chloride Substances 0.000 description 32
- 235000011164 potassium chloride Nutrition 0.000 description 32
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 30
- 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 24
- 239000011734 sodium Substances 0.000 description 24
- 229910052708 sodium Inorganic materials 0.000 description 24
- 239000000243 solution Substances 0.000 description 14
- 238000005868 electrolysis reaction Methods 0.000 description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 11
- 239000011591 potassium Substances 0.000 description 11
- 229960003975 potassium Drugs 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000005342 ion exchange Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000003518 caustics Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
【発明の詳細な説明】
(イ) 発明の目的
〔産業上の利用分野〕
本発明はカリウムイオンおよびナトリウムイオ
ンを含有する塩基性水溶液よりナトリウムイオン
を除去する方法、例えば塩化カリウム水溶液を電
解して水酸化カリウム水溶液を得る場合の原料で
ある塩化カリウムの塩基性水溶液中のナトリウム
イオンの除去、或はナトリウムイオン含有塩化カ
リウム水溶液を電解して得た水酸化カリウム中の
ナトリウムイオンの除去、その他、硫酸カリウ
ム、硝酸カリウム、炭酸カリウム、炭酸水素カリ
ウム、リン酸カリウム、リン酸水素カリウム、リ
ン酸２水素カリウム、等のカリウム塩含有塩基性
水溶液中に含まれるナトリウムイオンの除去等に
有効な精製法に関するものである。[Detailed Description of the Invention] (a) Purpose of the Invention [Field of Industrial Application] The present invention provides a method for removing sodium ions from a basic aqueous solution containing potassium ions and sodium ions, such as electrolyzing a potassium chloride aqueous solution. Removal of sodium ions in a basic aqueous solution of potassium chloride, which is a raw material for obtaining an aqueous potassium hydroxide solution, or removal of sodium ions in potassium hydroxide obtained by electrolyzing a sodium ion-containing aqueous potassium chloride solution, etc. Relating to a purification method effective for removing sodium ions contained in a basic aqueous solution containing potassium salts such as potassium sulfate, potassium nitrate, potassium carbonate, potassium hydrogen carbonate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, etc. It is something.
例えば水酸化カリウムは、塩化カリウム水溶液
を電解することにより工業的に生産されている
が、これによつて得た水酸化カリウム中には通常
0.1〜0.2％（重量％；以下同じ）程度のナトリウ
ムが水酸化ナトリウムの形で不純物として存在し
ている。これは原料である塩化カリウム中に塩化
ナトリウムが含まれ、このナトリウムイオンに起
因するもので、ナトリウムとカリウムは同族元素
であることから、電解においてほぼ同様の挙動を
示し、塩化カリウム水溶液中のナトリウムとカリ
ウムのモル比と同じモル比で電解を受けて水酸化
カリウム中に移行する。
For example, potassium hydroxide is industrially produced by electrolyzing a potassium chloride aqueous solution, but the potassium hydroxide obtained by this process usually contains
Approximately 0.1 to 0.2% (weight %; the same applies hereinafter) of sodium exists as an impurity in the form of sodium hydroxide. This is due to sodium chloride contained in the raw material potassium chloride, and this sodium ion.Since sodium and potassium are homologous elements, they behave almost the same in electrolysis, and the sodium chloride in the potassium chloride aqueous solution It undergoes electrolysis and migrates into potassium hydroxide in the same molar ratio as that of potassium and potassium.
工業的規模の塩化カリウム水溶液電解において
は、かゝるナトリウムイオンは通常除去されるこ
となくそのまゝ使用されているが、近年医業分野
や電子材料分野の急速な発展に伴い、これらに利
用されている水酸化カリウムもナトリウム含有量
の少いものが要求されるようになり、これに対処
することが必要となつて来ている。 In industrial-scale potassium chloride aqueous solution electrolysis, such sodium ions are usually used as they are without being removed, but in recent years, with the rapid development of the medical and electronic materials fields, they are being used in these fields. Potassium hydroxide, which is currently used in the industry, is now required to have a low sodium content, and it has become necessary to take measures to meet this demand.
塩化カリウム水溶液中からナトリウムイオンを
除去する方法としては、塩化ナトリウムと塩化カ
リウムの水に対する溶解度の差を利用する再結晶
法が知られており、又水和五酸化アンチモンを用
いてナトリウムイオン含有カリウム化合物を処理
することを骨子とするカリウム化合物の精製法が
特開昭49−45891号公報に示されている。 As a method for removing sodium ions from an aqueous solution of potassium chloride, a recrystallization method that utilizes the difference in solubility in water between sodium chloride and potassium chloride is known, and a method for removing sodium ions from a potassium chloride solution using hydrated antimony pentoxide is known. A method for purifying potassium compounds, which consists of treating the compounds, is disclosed in JP-A-49-45891.
上記の従来法において、再結晶法は、除去効率
が悪く、経済的ではなく、又工程も煩雑であり、
工業的規模では到底採用し難いものである。又、
特開昭49−45891号公報に示されている方法は、
その中に記載の水和五酸化アンチモンのアンチモ
ン含有量が81％と高く、結晶性も悪く、塩化カリ
ウム水溶液中はもとより、その電解生成物である
水酸化カリウム水溶液、さらには水中においても
アンチモンの溶出が認められる。
In the above conventional methods, the recrystallization method has poor removal efficiency, is not economical, and has a complicated process.
It is extremely difficult to adopt it on an industrial scale. or,
The method shown in Japanese Patent Application Laid-open No. 49-45891 is as follows:
The antimony content of the hydrated antimony pentoxide described therein is as high as 81%, and the crystallinity is also poor. Elution is observed.
本発明者等の経験によれば、濃度30％の水酸化
カリウム水溶液100部（重量部；以下同じ）に、
上記特許に示されている方法で得られた水和五酸
化アンチモン20部を加えて室温で６時間撹拌した
ところ、60〜110mg／のアンチモンの溶出が認
められ、塩化カリウム水溶液や水中においても20
〜50mg／のアンモチンの溶出が認められてい
る。 According to the experience of the present inventors, in 100 parts (parts by weight; the same applies hereinafter) of a potassium hydroxide aqueous solution with a concentration of 30%,
When 20 parts of hydrated antimony pentoxide obtained by the method described in the above patent was added and stirred at room temperature for 6 hours, 60 to 110 mg of antimony was eluted.
Elution of ~50 mg/ammotine was observed.
水酸化カリウム水溶液の溶出アンチモンは、水
酸化カリウムの利用に当つては不純物と考えられ
るため、これが事実上存在しないことが必要であ
り、この点からも上記水和五酸化アンチモンは実
用性に乏しいものである。 Antimony eluted from an aqueous potassium hydroxide solution is considered an impurity when potassium hydroxide is used, so it must be virtually absent.From this point of view, the above-mentioned hydrated antimony pentoxide is of little practical use. It is something.
本発明は、上記した電解の原料などとして使用
される塩化カリウム水溶液中のナトリウムイオ
ン、生成水酸化カリウム水溶液中のナトリウムイ
オン、その他、各種カリウム塩含有塩基性水溶液
中のナトリウムイオンを優れた性能を有する五酸
化アンチモンによつて分離除去する方法を提供す
るもので、実質的にナトリウムイオンを含まない
カリウム塩水溶液を効率よく得んとするものであ
る。 The present invention has excellent performance in removing sodium ions in potassium chloride aqueous solutions used as raw materials for electrolysis, sodium ions in generated potassium hydroxide aqueous solutions, and other sodium ions in various potassium salt-containing basic aqueous solutions. The present invention provides a method for separating and removing potassium salt using antimony pentoxide, which efficiently obtains an aqueous potassium salt solution that is substantially free of sodium ions.
(ロ) 発明の構成
〔問題点を解決するための手段〕
本発明はアンチモン含有量62〜75％の結晶性ア
ンチモン酸にカリウムイオンおよびナトリウムイ
オン含有塩基性水溶液を接触させてナトリウムイ
オンを除去する水溶液の精製法である。(B) Structure of the invention [Means for solving the problem] The present invention removes sodium ions by contacting crystalline antimonic acid with an antimony content of 62 to 75% with a basic aqueous solution containing potassium ions and sodium ions. This is a method for purifying aqueous solutions.
本発明に用いるアンチモン含有量62〜75％の結
晶性アンチモン酸は、水溶液での反応で得られた
水和五酸化アンチモンを鉱酸で熱成することによ
つて得られる。 The crystalline antimonic acid having an antimony content of 62 to 75% used in the present invention is obtained by thermally forming hydrated antimony pentoxide obtained by reaction in an aqueous solution with a mineral acid.
例えば金属アンチモンを王水に溶解後、多量の
水を添加し、加水分解させる方法、五塩化アンチ
モンを水中に添加し、加水分解させる方法などに
より得られたものであるが、この様にして得た水
和五酸化アンチモンは非晶質、もしくは非常に対
称性の悪い結晶であり、前記特開昭49−45891号
公報に記載の発明に使用される水和五酸化アンチ
モンがこれに該当する。この様な水和五酸化アン
チモンは、ナトリウムイオンに対するイオン交換
性を示すが水酸化カリウム水溶液、塩化カリウム
水溶液をはじめとするカリウム化合物水溶液や水
中でアンチモンが溶出することは前述の通りであ
る。 For example, antimony metal can be obtained by dissolving antimony metal in aqua regia and then adding a large amount of water for hydrolysis, or by adding antimony pentachloride to water and hydrolyzing it. The hydrated antimony pentoxide is amorphous or has very poor symmetry, and the hydrated antimony pentoxide used in the invention described in JP-A-49-45891 falls under this category. Such hydrated antimony pentoxide exhibits ion exchange properties for sodium ions, but as described above, antimony is eluted in aqueous potassium compound solutions such as aqueous potassium hydroxide and potassium chloride solutions, and in water.
本発明者等は、アンチモンの溶出について詳細
に検討した結果、溶出は結晶の程度と化学組成に
起因することを見出し、更に検討の結果、水和五
酸化アンチモンを、好ましくは酸濃度が0.1〜６
モル／の鉱酸、又は２種以上の鉱酸の混合物中
で30℃以上、80℃以下で５時間〜10日間維持する
ことにより熱成し、アンチモン含有量を62〜75％
の範囲に調整して得た結晶性アンチモン酸が、塩
化カリウム水溶液や水酸化カリウム水溶液、その
他のカリウム塩含有塩基性水溶液若しくは水中で
のアンチモンの溶出が１mg／以下となり、実用
に供しうることを確認したのである。 As a result of a detailed study on the elution of antimony, the present inventors found that the elution is caused by the degree of crystallization and chemical composition.As a result of further study, the inventors found that hydrated antimony pentoxide, preferably at an acid concentration of 0.1 to 6
It is thermally formed by maintaining the antimony content at 30℃ or higher and 80℃ or lower for 5 hours to 10 days in a mineral acid or a mixture of two or more types of mineral acids to reduce the antimony content to 62 to 75%.
It was confirmed that the crystalline antimonic acid obtained by adjusting the range of antimony in potassium chloride aqueous solution, potassium hydroxide aqueous solution, other potassium salt-containing basic aqueous solution, or water has antimony elution of 1 mg/or less and can be used for practical purposes. I confirmed it.
こゝで云う鉱酸とは、塩酸、硝酸、硫酸、リン
酸等であり、この熱成でアンチモン含有量を62〜
75％の範囲とすることにより安定した結晶性アン
チモン酸を得ることが出来る。 The mineral acids referred to here include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, etc., and this thermal formation reduces the antimony content to 62~
By setting it within the range of 75%, stable crystalline antimonic acid can be obtained.
アンチモン含有量が62％未満のもの、および75
％を越えた場合には本発明の目的に合致した結晶
性アンチモン酸とはならない。 Antimony content less than 62%, and 75
%, crystalline antimonic acid that meets the purpose of the present invention will not be obtained.
本発明に使用する結晶性アンチモン酸は、アン
チモンを主体とする化合物であればスズやチタン
等の他の金属を一部含有したものであつてもよ
く、かゝる結晶性アンチモン酸は粉末状、顆粒
状、繊維状等のいかなる形態でもよいが、粒状物
が最も好ましい。粒状物は結晶性アンチモン酸ケ
ーキを粉砕し、必要とする粒径のものを篩分けし
ても得られるが、使用時に破砕や粉化が生じ易い
ので有機系或は無機系の結合剤を用いて造粒した
ものが好ましい。 The crystalline antimonic acid used in the present invention may be a compound containing a portion of other metals such as tin or titanium as long as it is a compound mainly composed of antimony. , granules, fibers, etc., but granules are most preferred. Granules can be obtained by crushing a crystalline antimonic acid cake and sieving to obtain the required particle size, but since it tends to crush or powder during use, an organic or inorganic binder is used. It is preferable to use granules.
結晶性アンチモン酸に対するカリウムイオン、
ナトリウムイオン含有塩基性水溶液との接触方
法、その他として電解用のナトリウムイオン含有
塩化カリウムの塩基性水溶液について具体的に述
べれば、以下の通りである。 Potassium ion for crystalline antimonic acid,
The contact method with the basic aqueous solution containing sodium ions and the basic aqueous solution of potassium chloride containing sodium ions for electrolysis will be specifically described below.
先ず接触方法としては一般にバツチ法とカラム
法があるが、そのいずれの方法でもよい。 First, the contact method generally includes a batch method and a column method, and either method may be used.
例えばバツチ法で行う場合は、不純物であるナ
トリウムイオンの濃度により変動するが、通常は
塩化カリウムの塩基性水溶液100部に対して、結
晶性アンチモン酸を0.1〜50部、より好ましくは
0.5〜10部添加し、常温から90℃の温度範囲で１
〜24時間撹拌することにより不純物のナトリウム
を除去することができる。ここで撹拌は行なわな
くてもよいが、その場合は溶液の対流が悪くなる
ので、処理時間を多く要することもある。溶液の
温度は高いほどイオン交換速度が速くなるため、
処理時間は少なくて済むので好ましいが、90℃以
上では、加熱に多くのエネルギーを要し好ましく
ない。また溶液のPHであるが、PHが高いほどナト
リウムとの交換反応が促進されるため、アルカリ
性で行なうことが必要である。 For example, when using the batch method, the concentration varies depending on the concentration of impurity sodium ions, but usually 0.1 to 50 parts of crystalline antimonic acid is added to 100 parts of a basic aqueous solution of potassium chloride, more preferably 0.1 to 50 parts of crystalline antimonic acid.
Add 0.5 to 10 parts and 1 in the temperature range from room temperature to 90℃.
Impurity sodium can be removed by stirring for ~24 hours. Stirring may not be performed at this time, but in that case, the convection of the solution becomes poor, so that the processing time may be longer. The higher the temperature of the solution, the faster the ion exchange rate.
This is preferable because the processing time is short, but heating at 90° C. or higher is not preferable because it requires a lot of energy for heating. Regarding the pH of the solution, the higher the pH, the more the exchange reaction with sodium is promoted, so it is necessary to carry out the reaction under alkaline conditions.
たヾし塩化カリウム水溶液の電解により水酸化
カリウムを製造する工程では、通常すべて連続的
に行なわれているので、工程中でバツチ法にて行
なうのは必ずしも有利な方法とは言い難い。 However, since the process of producing potassium hydroxide by electrolysis of an aqueous potassium chloride solution is usually carried out continuously, it cannot necessarily be said that it is an advantageous method to carry out the process in batches.
このため工業的にはカラム法で行うことがより
好ましい。結晶性アンチモン酸の粒径は望ましく
は0.01〜５mm、特に望ましくは0.1〜２mmのもの
がよい。即ち0.01mm未満では圧力損失が大きく５
mmを越えると比表面積が小さく、イオン交換速度
が著しく低下する。体積速度は、塩化カリウムの
塩基性水溶液中のナトリウム濃度により変わる
が、好ましくは0.1〜100hr-1特に0.5〜20hr-1がよ
い。0.1hr-1以下では単位時間当りの処理量が少
なく、100hr-1以上では接触時間が短いため十分
に除去し切れない。 Therefore, from an industrial perspective, it is more preferable to use a column method. The particle size of the crystalline antimonic acid is preferably 0.01 to 5 mm, particularly preferably 0.1 to 2 mm. In other words, if it is less than 0.01 mm, the pressure loss will be large5
If it exceeds mm, the specific surface area will be small and the ion exchange rate will be significantly reduced. The volumetric rate varies depending on the sodium concentration in the basic aqueous solution of potassium chloride, but is preferably 0.1 to 100 hr -1 , particularly 0.5 to 20 hr -1 . If it is less than 0.1 hr -1 , the processing amount per unit time is small, and if it is more than 100 hr -1 , the contact time is too short to remove it sufficiently.
電解による水酸化カリウムの製造工程における
塩水精製系は、電解方法や、生成物の純度等によ
つて異るが、一般的には原塩溶解、硫酸根除去、
アルカリ土類金属除去、溶存塩素除去、PH調整
等、多くの工程が含まれている。本発明方法にお
けるナトリウム除去の工程はこれらの工程の内、
塩基性水溶液が処理される限り、いずれの工程間
で行つてもよい。以上により精製された塩化カリ
ウム水溶液を電解に供する場合の電気分解方法は
水銀法、イオン交換膜法、隔膜法のいずれでもよ
い。 The salt water purification system used in the process of producing potassium hydroxide by electrolysis varies depending on the electrolysis method and the purity of the product, but generally it involves dissolving raw salt, removing sulfate radicals,
It includes many processes such as alkaline earth metal removal, dissolved chlorine removal, and pH adjustment. The sodium removal step in the method of the present invention includes the following steps:
It may be carried out between any steps as long as the basic aqueous solution is treated. When the aqueous potassium chloride solution purified as described above is subjected to electrolysis, any of the mercury method, ion exchange membrane method, and diaphragm method may be used.
本発明に使用する結晶性アンチモン酸が、水和
五酸化アンチモンと異なり塩化カリ水溶液などに
対してアンチモンの溶解性を失なう理由は不明で
あるが、鉱酸中での熱成により結晶性が向上し、
又化学的安定性が増加するなどの理由が考えられ
る。
The reason why the crystalline antimonic acid used in the present invention, unlike hydrated antimony pentoxide, loses antimony solubility in an aqueous solution of potassium chloride is unknown, but it becomes crystalline due to thermal formation in a mineral acid. improved,
Another possible reason is that chemical stability increases.
本発明者等が上記の結晶性アンチモン酸につい
て0.1N水酸化カリウムを用いてそのイオン交換
容量を測定したところ、従来の水和五酸化アンチ
モンが１〜3meq／ｇであるのに対し、2.7〜
4meq／ｇであり、イオン交換性に優れているこ
とが判る。 When the present inventors measured the ion exchange capacity of the above-mentioned crystalline antimonic acid using 0.1N potassium hydroxide, it was 2.7 to 3 meq/g, whereas that of conventional hydrated antimony pentoxide was 1 to 3 meq/g.
4 meq/g, which indicates that it has excellent ion exchange properties.
以下に実施例、および参考例および比較参考例
を掲げて本発明を説明する。
The present invention will be described below with reference to Examples, Reference Examples, and Comparative Reference Examples.
実施例 １
金属アンチモン100部を王水750部に溶解して不
溶部分を別後、水4500部を添加すると水和五酸
化アンチモンが沈澱した。これを50℃で12時間保
持（熟成）した後、過、水洗後、100℃で10時
間乾燥した。Ｘ線回析、熱重量分析、示差熱分析
により、得られた生成物はSb2O54H2O（Sb含有量
62％）の組成で示される結晶性アンチモン酸であ
つた。また0.1N水酸化カリウム溶液でイオン交
換容量を測定したところ4.1meq／ｇであつた。Example 1 After dissolving 100 parts of antimony metal in 750 parts of aqua regia and separating the insoluble portion, 4500 parts of water was added to precipitate hydrated antimony pentoxide. This was maintained (ripened) at 50°C for 12 hours, filtered, washed with water, and dried at 100°C for 10 hours. X-ray diffraction, thermogravimetric analysis, and differential thermal analysis revealed that the obtained product was Sb 2 O 5 4H 2 O (Sb content
It was crystalline antimonic acid with a composition of 62%). Further, the ion exchange capacity was measured with a 0.1N potassium hydroxide solution and was found to be 4.1meq/g.
ナトリウムを500mg／、塩化カリを330ｇ／
含有する塩化カリウム水溶液に苛性カリウムを添
加することによりPH値を12に調整した水溶液100
部に上記方法で得られた結晶性アンチモン酸
（100〜200メツシユ）を２部添加し、60℃で24時
間撹拌した。結晶性アンチモン酸を別し、塩化
カリウム水溶液中のナトリウム濃度を測定したと
ころ、10mg／であつた。 Sodium 500mg/, potassium chloride 330g/
Aqueous solution 100 whose PH value was adjusted to 12 by adding caustic potassium to the potassium chloride aqueous solution containing
2 parts of crystalline antimonic acid (100 to 200 mesh) obtained by the above method were added to the mixture, and the mixture was stirred at 60°C for 24 hours. When the crystalline antimonic acid was separated and the sodium concentration in the potassium chloride aqueous solution was measured, it was found to be 10 mg/.
実施例 ２
五酸化アンチモン100部を水8000部中に添加す
ると水和五酸化アンチモンが沈澱した。これに塩
酸を添加し、酸濃度を3Nに調節した後、40℃で
72時間熱成した後、過、水洗後200℃で４時間
乾燥した。実施例と同様に分析したところ、
Sb2O5 1.8H2O（Sb含有量68％）の組成で示され
る結晶性アンチモン酸であり、イオン交換容量
は、3.8meq／ｇであつた。これをフツ素系樹脂
を結合剤とし、押し出し造粒法で粒状物（0.5〜
１mmφ）とした。Example 2 When 100 parts of antimony pentoxide was added to 8000 parts of water, hydrated antimony pentoxide precipitated. After adding hydrochloric acid to this and adjusting the acid concentration to 3N, it was heated at 40℃.
After heating for 72 hours, the mixture was filtered, washed with water, and dried at 200°C for 4 hours. When analyzed in the same manner as in the example,
It was crystalline antimonic acid with a composition of Sb 2 O 5 1.8H 2 O (Sb content 68%), and the ion exchange capacity was 3.8 meq/g. Using fluorine-based resin as a binder, this is made into granules (0.5~
1 mmφ).
この粒状物を50mmφ×500mmのガラスカラムに
充てんし、カラム内温度、50℃、SV＝5hr-1で実
施例と同じ塩化カリウム水溶液を通液したことろ
ナトリウム濃度は、４mg／以下となつた。通液
倍率250倍で破過したので再生を行ない再び塩化
カリウム水溶液を通液したことろ前回と同じイオ
ン交換容量を示した。以下吸着、再生のくり返し
て５回行なつても機能に変化はみられなかつた。 This granular material was packed into a 50 mmφ x 500 mm glass column, and the same potassium chloride aqueous solution as in the example was passed through the column at an internal temperature of 50°C and SV = 5 hr -1.The sodium concentration was 4 mg/or less. . Breakthrough was achieved at a liquid flow rate of 250 times, so regeneration was performed and potassium chloride aqueous solution was passed again, showing the same ion exchange capacity as the previous time. After repeated adsorption and regeneration five times, no change in function was observed.
実施例 ３
ナトリウムを1400mg／Kg含有する48％−苛性カ
リウム水溶液100部に、実施例１と同様にして得
られた結晶性アンチモン酸（100〜200メツシユ）
を５部添加し、60℃で24時間撹拌した。結晶性ア
ンチモン酸を濾別し、苛性カリウム水溶液中のナ
トリウム濃度を測定したことろ90mg／Kgであつ
た。Example 3 Crystalline antimonic acid obtained in the same manner as in Example 1 (100 to 200 mesh) was added to 100 parts of a 48% caustic potassium aqueous solution containing 1400 mg/Kg of sodium.
5 parts of were added and stirred at 60°C for 24 hours. The crystalline antimonic acid was filtered off, and the sodium concentration in the caustic potassium aqueous solution was determined to be 90 mg/Kg.
実施例 ４
実施例１と同様にして得られた結晶性アンチモ
ン酸（100〜200メツシユ）をガラスカラムに充填
し、カラム内温度70℃、SV＝0.2hr-1で、実施例
３と同じ苛性カリウム水溶液を通液したことろ、
ナトリウム濃度は20mg／Kgとなつた。通液倍率70
倍でナトリウム濃度が100mg／Kgとなつたので、
再生を行い、再び苛性カリウム水溶液を通液した
ところ、前回と同じイオン交換容量を示した。Example 4 Crystalline antimonic acid (100 to 200 mesh) obtained in the same manner as in Example 1 was packed in a glass column, and the same caustic as in Example 3 was prepared at a column internal temperature of 70°C and SV = 0.2 hr -1 . After passing potassium aqueous solution,
Sodium concentration was 20mg/Kg. Liquid flow magnification 70
Since the sodium concentration was doubled to 100mg/Kg,
When it was regenerated and aqueous caustic potassium solution was passed through it again, it showed the same ion exchange capacity as before.
実施例 ５
実施例１と同様にして得られた結晶性アンチモ
ン酸（100〜200メツシユ）をガラスカラムに充填
し、カラム内温度50℃、SV＝2hr-1で、ナトリウ
ムを500mg／、塩化カリウム350ｇ／含有する
塩化カリウム水溶液に苛性カリウムを添加するこ
とによりPH値を12に調整した水溶液を通液したと
ころ、通液倍率と流出液におけるナトリウム濃度
との関係は、図１の実線に示す通りであつた。Example 5 Crystalline antimonic acid (100 to 200 mesh) obtained in the same manner as in Example 1 was packed into a glass column, the column temperature was 50°C, SV = 2hr -1 , and sodium was added at 500mg/, potassium chloride was added. When an aqueous solution whose pH value was adjusted to 12 by adding caustic potassium to a potassium chloride aqueous solution containing 350 g/kg was passed through, the relationship between the flow rate and the sodium concentration in the effluent was as shown by the solid line in Figure 1. It was hot.
比較例 １
ガラスカラムに通液する水溶液として、ナトリ
ウムを500mg／、塩化カリウム350ｇ／含有す
る塩化カリウム水溶液に塩酸を添加することによ
りPH値を５に調整した水溶液を使用した以外は全
て実施例５と同様にして通液したところ、通液倍
率と流出液におけるナトリウム濃度との関係は、
図１の破線に示す通りであつた。Comparative Example 1 All examples were the same as in Example 5, except that the aqueous solution to be passed through the glass column was an aqueous solution containing 500 mg of sodium and 350 g of potassium chloride, the pH value of which was adjusted to 5 by adding hydrochloric acid. When the liquid was passed in the same manner as above, the relationship between the liquid passing magnification and the sodium concentration in the effluent was as follows.
It was as shown by the broken line in FIG.
参考例
実施例２で得た塩化ナトリウム水溶液を用いて
以下の条件でイオン交換膜電解を実施した。Reference Example Ion exchange membrane electrolysis was carried out using the sodium chloride aqueous solution obtained in Example 2 under the following conditions.
電解槽膜 1dm2デユポン社製NAFION90209
陽 極 Ti製ラス鋼に貴金属コーテイングした
もの
陰 極 Fe基材の表面を活性化させたもの
陽極室へ供給する塩化カリウム水溶液は電槽出
口濃度が160〜240ｇ／のKCl濃度の範囲になる
ように供給し、陰極室へは純水をKOH濃度31％
を目標としてで供給した。電槽は温度85℃にラン
プにより加熱され電流密度30A／ｄm3で40日間運
転した、運転終了10日間の槽電圧は3.1〜3.3V陰
極電流効率94〜97％であつた。Electrolytic cell membrane 1dm 2NAFION90209 manufactured by DuPont Anode Ti lath steel coated with precious metal Cathode Fe base material surface activated The potassium chloride aqueous solution supplied to the anode chamber has a concentration of 160 to 240 g at the outlet of the cell Pure water is supplied to the cathode chamber with a KOH concentration of 31%.
was supplied as a target. The cell was heated to a temperature of 85 DEG C. by a lamp and operated for 40 days at a current density of 30 A/dm 3 .The cell voltage during the final 10 days of operation was 3.1 to 3.3 V and a cathode current efficiency of 94 to 97%.
生成KOH溶液中のナトリウム濃度は５mg／
以下またはアンチモン濃度は検出限界以下であ
り、目的とする低ナトリウム苛性カリウム水溶液
が得られた。 The sodium concentration in the produced KOH solution is 5mg/
The antimony concentration was below the detection limit, and the desired low sodium caustic potassium aqueous solution was obtained.
比較参考例
実施例１，２で使用した末処理の塩化カリウム
溶液を用い実施例２と同じ電解方法により電解し
た。生成KOH溶液中のナトリウム濃度は630mg／
となつた。Comparative Reference Example Electrolysis was carried out using the same electrolytic method as in Example 2 using the final treated potassium chloride solution used in Examples 1 and 2. The sodium concentration in the produced KOH solution is 630mg/
It became.
(ハ) 発明の効果
以上の本発明によれば、例えば工業的な水酸化
カリウムの製造原料として使用される塩化カリウ
ム水溶液中のナトリウム分を、特定のアンチモン
含有量の結晶性アンチモン酸を用いて接触させる
ことにより容易かつ効率よく除去することが出
来、これにより得た水酸化カリウム水溶液中のナ
トリウム分は大巾に減少し、医薬、電子材料等の
各分野で要求されている高純度水酸化カリウムの
工業的で容易な製造を可能とするものである。(c) Effects of the Invention According to the present invention, the sodium content in an aqueous potassium chloride solution used as a raw material for producing industrial potassium hydroxide, for example, can be reduced by using crystalline antimonic acid with a specific antimony content. It can be easily and efficiently removed by contacting the potassium hydroxide solution, and the sodium content in the obtained potassium hydroxide aqueous solution is greatly reduced, resulting in high-purity hydroxide, which is required in various fields such as medicine and electronic materials. This enables industrial and easy production of potassium.
又本発明に使用する結晶性アンチモン酸はカリ
ウム塩水溶液中でのアンチモンの溶出を生ずるこ
となく、優れた選択性をもつてナトリウムイオン
を除去することが出来るもので、本発明はこの点
においても優れたものである。 Furthermore, the crystalline antimonic acid used in the present invention can remove sodium ions with excellent selectivity without causing the elution of antimony in an aqueous potassium salt solution, and the present invention also has advantages in this respect. It is excellent.
本発明は、前記電解における原料塩化カリウム
水溶液中のナトリウムイオンの除去のみならずナ
トリウムイオン含有塩化カリウム水溶液の電解で
生成した水酸化カリウム中のナトリウムイオンの
除去、その他、硫酸カリウム、硝酸カリウム、炭
酸カリウム、炭酸水素カリウム、リン酸カリウ
ム、リン酸水素カリウム、リン酸２水素カリウム
等の各種カリウム塩水溶液中のナトリウムイオン
の除去に対しても充分にその威力を発揮すること
が出来、利用価値大なるものである。 The present invention not only removes sodium ions from the raw potassium chloride aqueous solution in the electrolysis, but also removes sodium ions from potassium hydroxide generated by the electrolysis of the sodium ion-containing potassium chloride aqueous solution, as well as potassium sulfate, potassium nitrate, and potassium carbonate. It can fully demonstrate its power in removing sodium ions from various potassium salt aqueous solutions such as potassium hydrogen carbonate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, etc., and has great utility value. It is something.
図１は、実施例５及び比較例１における通液倍
率と流出液中のナトリウム濃度との関係を示す図
であり、図中の実線は実施例５の結果を示し、図
中の破線は比較例１の結果を示す。
FIG. 1 is a diagram showing the relationship between the liquid flow rate and the sodium concentration in the effluent in Example 5 and Comparative Example 1. The solid line in the diagram shows the results of Example 5, and the broken line in the diagram shows the comparison. The results of Example 1 are shown.
Claims (1)
有する塩基性水溶液からナトリウムイオンを除去
するに当り、該水溶液をアンチモン含有量62〜75
重量％の結晶性アンチモン酸に接触させることを
特徴とする水溶液の精製法。1. When removing sodium ions from a basic aqueous solution containing potassium ions and sodium ions, the aqueous solution has an antimony content of 62 to 75
A method for purifying an aqueous solution, characterized in that it is brought into contact with % by weight of crystalline antimonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12843884A JPS6110025A (en) | 1984-06-23 | 1984-06-23 | Purification of aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12843884A JPS6110025A (en) | 1984-06-23 | 1984-06-23 | Purification of aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6110025A JPS6110025A (en) | 1986-01-17 |
| JPH048373B2 true JPH048373B2 (en) | 1992-02-14 |
Family
ID=14984735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12843884A Granted JPS6110025A (en) | 1984-06-23 | 1984-06-23 | Purification of aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6110025A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4859343A (en) * | 1987-12-02 | 1989-08-22 | Lithium Corporation Of America | Sodium removal from brines |
| JP5692463B2 (en) * | 2012-09-18 | 2015-04-01 | 旭硝子株式会社 | Molten salt for glass strengthening |
| CN111928518A (en) * | 2020-08-10 | 2020-11-13 | 江苏富来尔科技发展有限公司 | Method for removing potassium and sodium ions in regenerated lithium bromide solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4830000A (en) * | 1971-08-24 | 1973-04-20 | ||
| JPS4945891A (en) * | 1972-09-07 | 1974-05-01 |
-
1984
- 1984-06-23 JP JP12843884A patent/JPS6110025A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4830000A (en) * | 1971-08-24 | 1973-04-20 | ||
| JPS4945891A (en) * | 1972-09-07 | 1974-05-01 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6110025A (en) | 1986-01-17 |
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