JPH026844A - Synthetic lithium adsorbent and production thereof - Google Patents
Synthetic lithium adsorbent and production thereofInfo
- Publication number
- JPH026844A JPH026844A JP15739488A JP15739488A JPH026844A JP H026844 A JPH026844 A JP H026844A JP 15739488 A JP15739488 A JP 15739488A JP 15739488 A JP15739488 A JP 15739488A JP H026844 A JPH026844 A JP H026844A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- oxide
- compd
- adsorbent
- synthetic
- 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.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 58
- 239000003463 adsorbent Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- BZHNHDOWFCBZNK-UHFFFAOYSA-N antimony lithium Chemical compound [Li].[Sb] BZHNHDOWFCBZNK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 150000001463 antimony compounds Chemical class 0.000 abstract 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 abstract 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001947 lithium oxide Inorganic materials 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910000410 antimony oxide Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 150000002642 lithium compounds Chemical class 0.000 description 5
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 seawater Chemical compound 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000006163 transport media Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は種々の金属イオンを含有する溶液から選択的に
リチウムを吸着する新規の合成リチウム吸着剤およびそ
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel synthetic lithium adsorbent that selectively adsorbs lithium from solutions containing various metal ions, and a method for producing the same.
リチウムは多くの分野、例えば電池、ガラス、セラミッ
クス、航空機用のＡＩ／Ｌ＋合金などに用いられている
。将来は核融合燃料、核融合炉の熱の運搬媒体あるいは
冷却剤としての需要が見込まれており、リチウムの消費
量は著しく増大すると考えられている（日本鉱業会誌、
第９７巻、２２１． １９８１）。現在リチウムの生産
はアメリカ合衆国が全世界の約７０％を占め寡占状態に
あるが、我国はリチウム鉱石資源に乏しく全量を輸入に
依存している。Lithium is used in many fields, such as batteries, glass, ceramics, and AI/L+ alloys for aircraft. In the future, lithium consumption is expected to increase significantly as demand for fusion fuel, heat transport medium or coolant in fusion reactors is expected (Journal of the Japan Mining Industry Association,
Volume 97, 221. 1981). Currently, the United States has an oligopoly on lithium production, accounting for approximately 70% of the world's production, but Japan lacks lithium ore resources and relies entirely on imports.
しかるに、我国においても海水あるいは比較的豊富に存
在する地熱熱水や温泉水には低濃度ではあるがリチウム
を含有する場合が多く、これらのリチウムを含む希薄溶
液から該リチウムを効率よく回収するための高性能リチ
ウム吸着剤の開発が強く要望されている。However, even in Japan, seawater or relatively abundant geothermal hot water and hot spring water often contain lithium, albeit at a low concentration, and it is difficult to efficiently recover lithium from dilute solutions containing lithium. There is a strong demand for the development of high-performance lithium adsorbents.
従来、リチウムを含む希薄溶液からの該、リチウムの吸
着剤としては、無定形含水酸化アルミニウム（海水誌、
第３２巻、 ７８． １９７８）、含水酸化スズ（日
本鉱業会誌、第３９巻、 ９３３． １９８３）、ア
ンチモン酸スズ（Ｈｙｄｒｏｍｅｔａｌｌｕｒｇｙ、
１２．８３．１９８４）、層状チタン酸塩（Ｊ、 Ｐ！
１ｙ、 Ｃｈｅｍ、、 ８８．５０２３．１９８２）、
二酸化マンガン（日本鉱業会誌、第１０２巻、 ３０
７． １９８６）、λ型マンガン酸化物（Ｎｅｏｒｇ、
Ｍａｔｅｒ、９．１０４１゜１９７３； ５ｏｌｖ、
Ｅｘｔｒ、 Ｊｏｎ Ｅｘｃｈ、、 ５．５６１．１
９８７）などが報告されている。Conventionally, as an adsorbent for lithium from a dilute solution containing lithium, amorphous hydrated aluminum oxide (Kaisui Journal,
Volume 32, 78. 1978), hydrous tin oxide (Journal of the Japan Mining Association, Vol. 39, 933. 1983), tin antimonate (Hydrometallurgy,
12.83.1984), layered titanates (J, P!
1y, Chem, 88.5023.1982),
Manganese dioxide (Journal of the Japan Mining Association, Vol. 102, 30
7. 1986), λ-type manganese oxide (Neorg,
Mater, 9.1041°1973; 5olv,
Extr, Jon Exch, 5.561.1
987) etc. have been reported.
しかしながら、前述の吸着剤はλ型マンガン酸化物を除
いてはいずれも吸着容量がかなり小さいため実用性に乏
しいと考えられる。また、λ型マンガン酸化物において
は８０°Ｃ以上の高温水溶液中ではその結晶構造が崩壊
して吸着容量が大幅に低下する欠点を存する。However, all of the above-mentioned adsorbents, except for λ-type manganese oxide, have considerably small adsorption capacities and are therefore considered to be of little practical use. Furthermore, λ-type manganese oxide has the disadvantage that its crystal structure collapses in a high-temperature aqueous solution of 80° C. or higher, resulting in a significant decrease in adsorption capacity.
リチウムを含む海水、地熱熱水及び温泉水など種々の希
薄溶液から該リチウムを実用的に回収するためには、溶
存量の多いナトリウム、カリウム、カルシウム、マグネ
シウムなど他の共存陽イオンよりリチウムに対する選択
性に優れ、しかもその吸着容量が大きく、且つ耐熱性の
高い新規吸着剤の開発が要請されている。In order to practically recover lithium from various dilute solutions such as seawater, geothermal hot water, and hot spring water containing lithium, it is necessary to select lithium over other coexisting cations such as sodium, potassium, calcium, and magnesium, which have large dissolved amounts. There is a need for the development of a new adsorbent that has excellent properties, a large adsorption capacity, and high heat resistance.
本発明の目的は、前述のような要件を満足しうる実用性
の高い合成リチウム吸着剤およびその製造方法を提供す
ることにある。An object of the present invention is to provide a highly practical synthetic lithium adsorbent that can satisfy the above-mentioned requirements and a method for producing the same.
本発明者らはリチウム回収に関して長年鋭意研究を重ね
た結果、ある種のりチウム−アンチモン複合酸化物を酸
処理したものが上記目的に適合することを見い出し、新
規の合成リチウム吸着剤およびその製造方法の発明に至
った。As a result of many years of intensive research into lithium recovery, the present inventors discovered that a certain type of lithium-antimony composite oxide treated with acid is suitable for the above purpose, and developed a new synthetic lithium adsorbent and its manufacturing method. This led to the invention of
すなわち、この発明は一般式Ｌｉ＋−，ＨｘＳｂＯａ（
式中のＸの値はＯ＜ｘ＜１）で表わされる合成リチウム
吸着剤およびその製造方法に関する。That is, this invention has the general formula Li+-, HxSbOa (
The value of X in the formula relates to a synthetic lithium adsorbent represented by O<x<1) and a method for producing the same.
次に本発明の合成リチウム吸着剤およびその製造方法に
ついて述べる。本発明の合成リチウム吸着剤はＬＩＳｂ
Ｏｓの理想組成を有するリチウム−アンチモン複合酸化
物を酸で処理してリチウムを溶出させることにより得ら
れる。原料となるリチウム−アンチモン複合酸化物はリ
チウム化合物とアンチモン酸化物の混合粉末を５００°
〜１０００°Ｃの所定温度で加熱処理することにより製
造できる。使用されるリチウム化合物としては、例えば
炭酸塩、硝酸塩、塩化物酸化物などをあげることができ
る。Next, the synthetic lithium adsorbent of the present invention and its manufacturing method will be described. The synthetic lithium adsorbent of the present invention is LISb
It is obtained by treating a lithium-antimony composite oxide having an ideal composition of Os with an acid to elute lithium. The raw material, lithium-antimony composite oxide, is prepared by heating a mixed powder of lithium compound and antimony oxide at 500°.
It can be manufactured by heat treatment at a predetermined temperature of ~1000°C. Examples of the lithium compounds used include carbonates, nitrates, chloride oxides, and the like.
これらは市販の粉末物をそのまま用いることができる。Commercially available powders can be used as they are.
また、アンチモン酸化物としては、例えば原子価が３価
、４価、５価の市販の粉末状アンチモン酸化物が使用で
きる。リチウムとアンチモンの原子比が１＝ １になる
ように上記いずれかのリチウム化合物とアンチモン酸化
物を充分に粉砕混合し、該混合物を５００° 〜１０Ｇ
０°Ｃの範囲の所定温度で加熱処理することによってＬ
ＩＳｂＯｓの組成を有するリチウム−アンチモン複合酸
化物が得られる。Further, as the antimony oxide, for example, commercially available powdered antimony oxides having a valence of 3, 4, or 5 can be used. Thoroughly grind and mix any of the above lithium compounds and antimony oxide so that the atomic ratio of lithium and antimony is 1=1, and heat the mixture at 500° to 10G.
L by heat treatment at a predetermined temperature in the range of 0°C.
A lithium-antimony composite oxide having a composition of ISbOs is obtained.
Ｌｌ／Ｓｂ比は理想的には１であることが望ましいが０
．５から１．５の間の値は許容される。該複合酸化物を
酸溶液で洗浄処理し、複合酸化物中のリチウムを溶出さ
せることにより本発明の合成リチウム吸着剤が得られる
。リチウムを溶出させるために用いる酸溶液は、酸溶液
であればよいが、望ましくはｐＨ１以下の塩酸、硫酸、
硝酸などの鉱酸溶液がよい。本発明の合成リチウム吸着
剤の生成はＸ線粉末回折により容易に確認することがで
きる。すなわち、ＣｕＫαのＸ線を用いた場合、２θで
１９．８．２１．３．３２．８および４０．７’に特徴
的な回折線が出現し、新規物質であると考えられる。Ideally, the Ll/Sb ratio is 1, but it is 0.
．． Values between 5 and 1.5 are acceptable. The synthetic lithium adsorbent of the present invention can be obtained by washing the composite oxide with an acid solution and eluting lithium in the composite oxide. The acid solution used to elute lithium may be any acid solution, but preferably hydrochloric acid, sulfuric acid, or
Mineral acid solutions such as nitric acid are preferred. The production of the synthetic lithium adsorbent of the present invention can be easily confirmed by X-ray powder diffraction. That is, when CuKα X-rays are used, characteristic diffraction lines appear at 19.8.21.3.32.8 and 40.7' at 2θ, and it is considered to be a new substance.
本発明の合成リチウム吸着剤を溶液中で用いた場合リチ
ウム吸着容量が大きく、かつリチウム選択性が高く非常
に優れたリチウム吸着特性を示す。When the synthetic lithium adsorbent of the present invention is used in a solution, it has a large lithium adsorption capacity, high lithium selectivity, and exhibits excellent lithium adsorption properties.
リチウムに対する選択性は出発原料のアンチモン酸化物
のみを上記の製造条件下で処理したものが吸着能を全く
示さないことから、リチウム−アンチモン複合酸化物か
らリチウムを溶出させた本吸着剤特有の吸着能に基づく
ものと考えられる。Regarding the selectivity for lithium, when only the starting material, antimony oxide, was treated under the above production conditions, it showed no adsorption ability at all. It is thought to be based on Noh.
本発明により得られる吸着剤は、他の金属イオンを含む
海水、地熱熱水および温泉水など低濃度リチウムを含む
溶液からリチウムを選択的に回収するのに好適に使用す
ることができる。The adsorbent obtained by the present invention can be suitably used to selectively recover lithium from solutions containing low concentrations of lithium, such as seawater, geothermal hot water, and hot spring water containing other metal ions.
次に実施例によって本発明をさらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例１
炭酸リチウム特級試薬１．１１ｇと二酸化アンチモン特
級試薬４．３８ｇを用い、拙シ寺機にて充分に粉砕、混
合したものを出発原料とした。これを電気マツフル炉中
で６５０°Ｃ１２４時間加熱処理を行った。得られた加
熱生成物を０．５モル塩酸溶液１００ｍ１中に入れ５０
°Ｃで３日間反応させリチウムを溶出させた。蒸留水で
洗浄後、５０ ’Ｃで乾燥して本発明製品を得た。Example 1 1.11 g of a special grade lithium carbonate reagent and 4.38 g of a special grade antimony dioxide reagent were thoroughly ground and mixed using a sushi machine, and this was used as a starting material. This was heat-treated in an electric Matsufuru furnace at 650°C for 124 hours. The heated product obtained was placed in 100 ml of 0.5 molar hydrochloric acid solution and
The reaction was carried out at °C for 3 days to elute lithium. After washing with distilled water, the product was dried at 50'C to obtain a product of the present invention.
本発明製品１００ｍｇをｐＨ８，５の金属イオン混合溶
液（０，５モル塩化アンモニウム溶液と０．５モル水酸
化アンモニウム溶液からなるｐＨ８，５のｐＨ緩衝液中
に、それぞれの金属イオン濃度が１ミリモルとなるよう
に特級試薬の塩化リチウム、塩化カリウム、塩化ナトリ
ウム、塩化カルシウムを添加して調製用００ｍ１ととも
に２５°Ｃの恒温水槽中で２週間振とうしたのち、孔径
０．４５．ｔＬ７ｎのメンブランフィルタ−で固液を分
離した。液相中の金属イオン濃度を原子吸光法で測定し
、吸着前後の濃度差よりそれぞれの金属イオンの吸着量
を算出した。各金属イオンの選択性を表わす指標の分配
係数は平衡吸着量（ｍｇ／＋ｎ＋）を溶液中の平衡濃度
（ｍｇ／ｍｌ）で除することにより求められ、リチウム
＝３１９０、ナトリウム＝８０１ カリウム＝３０お
よびカルシウム＝１３０であり、リチウムに対し優れた
選択性を示すことが判明した。100 mg of the product of the present invention was added to a mixed metal ion solution of pH 8.5 (a pH buffer solution of pH 8.5 consisting of a 0.5 molar ammonium chloride solution and a 0.5 molar ammonium hydroxide solution, with a concentration of each metal ion of 1 mmol). Add special grade reagents such as lithium chloride, potassium chloride, sodium chloride, and calcium chloride, and shake for 2 weeks in a constant temperature water bath at 25°C with 00ml for preparation, then filter with a membrane filter with a pore size of 0.45.tL7n The solid-liquid was separated at -.The metal ion concentration in the liquid phase was measured by atomic absorption spectrometry, and the adsorption amount of each metal ion was calculated from the difference in concentration before and after adsorption. The partition coefficient is determined by dividing the equilibrium adsorption amount (mg/+n+) by the equilibrium concentration in the solution (mg/ml), and the following formulas are obtained: lithium = 3190, sodium = 801, potassium = 30, and calcium = 130. It was found to exhibit excellent selectivity.
実施例２ 実施例１と同様に操作して本発明製品を得た。Example 2 A product of the present invention was obtained in the same manner as in Example 1.
但し、電気マツフル炉中の温度を５５０℃とした。本発
明製品を用い、実施例１で用いた金属イオン混合溶液か
らのリチウムイオンの吸着平衡到達時間及び平衡吸着量
を２５℃、５５°Ｃ１９０°Ｃの各温度で測定した結果
を第１表に示す。However, the temperature in the electric Matsufuru furnace was 550°C. Table 1 shows the results of measuring the adsorption equilibrium time and equilibrium adsorption amount of lithium ions from the metal ion mixed solution used in Example 1 using the product of the present invention at temperatures of 25°C, 55°C, and 190°C. show.
第１表リチウム吸着特性と吸着温度の関係第１表から明
らかなように、本発明製品ではリチウムの吸着平衡に達
する時間は、２５°Ｃで２４０時間であるが９０’Ｃで
は３時間と吸着温度の上昇に伴い急激に短縮されている
。一方、リチウムの平衡吸着量は２５°〜９０°Ｃの測
定温度範囲では殆ど変化が認められず、λ型マンガン酸
化物より耐熱性に優れていることがわかる。Table 1 Relationship between lithium adsorption characteristics and adsorption temperature As is clear from Table 1, the time required for the product of the present invention to reach lithium adsorption equilibrium is 240 hours at 25°C, but only 3 hours at 90°C. It is rapidly shortening as the temperature rises. On the other hand, the equilibrium adsorption amount of lithium shows almost no change in the measurement temperature range of 25° to 90°C, indicating that it has better heat resistance than λ-type manganese oxide.
比較例１
リチウム化合物を存在させることなく、他は実施例１と
同じ条件で三酸化アンチモンのみを加熱、酸処理、水洗
、乾燥を行い、該乾燥物を用いて実施例１と同じ条件で
吸着実験を行った。その結果、リチウムのみならず他の
金属イオンについても吸着前後の溶液中の濃度変化は全
く認められず、金属イオンの１汲着が起こらないことが
わかった。以上のことから、本発明の製造方法において
、リチウム化合物は、リチウム選択性の著しく高い陽イ
オン吸着特性の発現に大きく寄与していることは明らか
である。Comparative Example 1 Only antimony trioxide was heated, acid-treated, washed with water, and dried under the same conditions as Example 1 without the presence of a lithium compound, and the dried product was used for adsorption under the same conditions as Example 1. We conducted an experiment. As a result, no change in the concentration of not only lithium but also other metal ions in the solution before and after adsorption was observed, indicating that no single adsorption of metal ions occurred. From the above, it is clear that in the production method of the present invention, the lithium compound greatly contributes to the development of cation adsorption characteristics with extremely high lithium selectivity.
比較例２
実施例１および２の本発明製品と公知の合成法によって
製造したλ型マンガン酸化物を用い、実施例１と同一条
件で行ったリチウム吸着実験の結果の比較を表２に示す
。Comparative Example 2 Table 2 shows a comparison of the results of a lithium adsorption experiment conducted under the same conditions as Example 1 using the products of the present invention of Examples 1 and 2 and a λ-type manganese oxide produced by a known synthesis method.
＊α（分離係数＝リチウムの分配係数／カルシウムの分
配係数）第２表から明らかなように、従来量も優れたリ
チウム吸着剤とされているλ型マンガン酸化物に比べ本
発明製品（実施例２）のリチウムの分配係数の値は約３
４７倍と著しく大きい。さらにリチウムについで選択性
の高いカルシウムの影響についてみると、分離係数αの
値は本発明製品（実施例２）の場合６０．０であるのに
対し、λ型マンガン酸化物では１５．１と小さく、リチ
ウム回収時における共存カルシウムの影響も本発明製品
のほうがはるかに小さいことが明らかである。*α (Separation coefficient = Partition coefficient of lithium/Partition coefficient of calcium) As is clear from Table 2, the product of the present invention (Example The value of the distribution coefficient of lithium in 2) is approximately 3
It is significantly larger at 47 times. Furthermore, looking at the influence of calcium, which has high selectivity next to lithium, the value of separation coefficient α is 60.0 in the case of the product of the present invention (Example 2), whereas it is 15.1 in the case of the λ-type manganese oxide. It is clear that the influence of coexisting calcium during lithium recovery is also much smaller in the product of the present invention.
Claims (1)
ｘの値は０＜ｘ＜１である）で表わされる合成リチウム
吸着剤。 ２）リチウムとアンチモンの複合酸化物から酸でリチウ
ムを溶出することを特徴とする特許請求の範囲第１項記
載の一般式で表わされる合成リチウム吸着剤の製造方法
。[Claims] 1) A synthetic lithium adsorbent represented by the general formula Li_1_-_xH_xSbO_3 (the value of x in the formula is 0<x<1). 2) A method for producing a synthetic lithium adsorbent represented by the general formula according to claim 1, which comprises eluting lithium from a composite oxide of lithium and antimony with an acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15739488A JPH026844A (en) | 1988-06-24 | 1988-06-24 | Synthetic lithium adsorbent and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15739488A JPH026844A (en) | 1988-06-24 | 1988-06-24 | Synthetic lithium adsorbent and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH026844A true JPH026844A (en) | 1990-01-11 |
| JPH0525540B2 JPH0525540B2 (en) | 1993-04-13 |
Family
ID=15648674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15739488A Granted JPH026844A (en) | 1988-06-24 | 1988-06-24 | Synthetic lithium adsorbent and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH026844A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0283217A (en) * | 1988-09-19 | 1990-03-23 | Mitsuo Abe | Method for synthesizing monoclinic antimonic acid and method for selective separaiton of lithium using the same |
| CN107128955A (en) * | 2017-05-15 | 2017-09-05 | 李陇岗 | A kind of method that lithium carbonate is extracted from thermal water |
-
1988
- 1988-06-24 JP JP15739488A patent/JPH026844A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0283217A (en) * | 1988-09-19 | 1990-03-23 | Mitsuo Abe | Method for synthesizing monoclinic antimonic acid and method for selective separaiton of lithium using the same |
| JPH059374B2 (en) * | 1988-09-19 | 1993-02-04 | Mitsuo Abe | |
| CN107128955A (en) * | 2017-05-15 | 2017-09-05 | 李陇岗 | A kind of method that lithium carbonate is extracted from thermal water |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0525540B2 (en) | 1993-04-13 |
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