CN1055677C - 从铯矾制备铯盐的方法 - Google Patents
从铯矾制备铯盐的方法 Download PDFInfo
- Publication number
- CN1055677C CN1055677C CN94191890A CN94191890A CN1055677C CN 1055677 C CN1055677 C CN 1055677C CN 94191890 A CN94191890 A CN 94191890A CN 94191890 A CN94191890 A CN 94191890A CN 1055677 C CN1055677 C CN 1055677C
- Authority
- CN
- China
- Prior art keywords
- cesium
- calcium
- caesium
- alum
- reaction
- 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
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 239000004411 aluminium Substances 0.000 title claims description 3
- 229940037003 alum Drugs 0.000 title 1
- 150000001663 caesium Chemical class 0.000 title 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 159000000007 calcium salts Chemical class 0.000 claims abstract 3
- VHUJINUACVEASK-UHFFFAOYSA-J aluminum;cesium;disulfate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Cs+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VHUJINUACVEASK-UHFFFAOYSA-J 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- YRAMACNQEYDINL-UHFFFAOYSA-J aluminum;cesium;disulfate Chemical compound [Al+3].[Cs+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YRAMACNQEYDINL-UHFFFAOYSA-J 0.000 abstract description 3
- 159000000006 cesium salts Chemical class 0.000 abstract 1
- -1 Cesium compound Chemical class 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical class [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 3
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D17/00—Rubidium, caesium or francium compounds
Abstract
本发明涉及一种从铯矾制备铯盐的方法，该方法是在一单一容器中，在水存在下使铯矾与氢氧化钙反应，氢氧化钙的用量与铯矾中的铝的摩尔数相等，并使铯矾与易溶于水的钙盐反应，易溶于水的钙盐的摩尔用量与铯矾中的摩尔数相等，采用过滤或离心分离的房与铯矾中的铝的摩尔数相等，并使铯矾与易溶于水的钙盐反应，易溶于水的钙盐的摩尔用量与铯矾中的铯的摩尔数相等，采用过滤或离心分离的方法分离出氢氧化铝和硫酸钙沉淀。
Description
本发明涉及一种从铯矾制备铯盐的方法。
美国专利3,489,509公开了一种制备具有高纯度的铯化合物的方法。该方法中，铯矾(cesium-aluminum-alum)用氢氧化钡处理，接着与二氧化碳反应。随后加入化学计量的卤化钡，以得到纯卤化铯。为了从铯矾得到卤化铯，需要使用氢氧化钡和卤化钡，这将导致费用高昂，并且要发生与二氧化碳的中和反应。
本发明的一个目的是提供一种能克服如上所述的缺点的方法。
按照本发明，上述目的是这样达到的：在一单一容器中，将铯矾与摩尔用量与铯矾中的铝的摩尔数相等的氢氧化钙、以及摩尔用量与铯矾中的铯的摩尔数相等的水溶性钙盐反应，经过滤或离心分离分离出氢氧化铝和硫酸钙沉淀。在本发明的方法中，不使用比钙化合物昂贵的钡化合物，并且不用进行与二氧化碳的中和反应；其一个进一步的优点是，由反应直接得到的铯盐溶液的浓度大于10％。这将大大降低在制备浓缩的铯盐溶液以及在制备固体盐的过程中从溶液中除去水的工作量。
对于按照下述方程式使铯矾与化学计量的氢氧化钙的直接反应是周知的，但是该反应不能以很满意的收率得到氢氧化铯。这可能是因为产生的氢氧化铝和石膏沉淀掩蔽了悬浮的氢氧化钙的表面，以致于其不能参与反应。另一方面，也不能通过使用氢氧化钙来补偿被掩蔽的氢氧化钙，因为补加的氢氧化钙的量必须精确控制方能避免目的产物氢氧化铯的被污染，而被污染的产品中的氢氧化钙很难除去。因为这一原因，本领域中通常是使用氢氧化钡；其更易溶于水但也非常昂贵。
采用本发明的方法，令人惊奇地发现，可在一单一的容器中制备出纯的铯盐。甲酸钙、乙酸钙、柠檬酸钙、氯化钙或溴化钙可用作所述的水溶性钙盐。
优选是以以下方式从铯矾制备铯盐：所述的反应在80～120℃的范围内进行，并且在反应开始时，悬浮液的每升水中的不溶性固体物为100～500克。所述的不溶性固体物由反应开始时不溶的那部分Ca(OH)2、铯盐和铯矾所组成。
下面用下述实施例更详细地说明本发明。实施例1 甲酸铯的制备
向一可加热和可搅拌的容积为500升的容器中加入290升水、17千克氧化钙和13千克甲酸钙。将得到的悬浮液在搅拌下加热至其沸点，然后加入111千克铯矾。将反应混合物在其沸点温度搅拌2小时，随后将其冷却和过滤。滤液含有约11％的甲酸铯、0.1％的钙离子、0.05％的铝离子和1％的硫酸根离子。滤渣再用水洗涤。在合并的滤液中检测出约有95％的原料中的铯被转化成了甲酸铯。实施例2 乙酸铯的制备
使用与实施例1中相类似的容器，只是其容积为1000升。向其中加入375千克水、43.8千克氧化钙和45.8千克乙酸钙。将得到的悬浮液加热至其沸点，然后加入296千克铯矾。随后将该悬浮液在其沸点温度下搅拌2小时并使其冷却，然后过滤。得到的溶液中含有约20％的乙酸铯，其中含有58％的原料中的铯。将滤渣再洗涤，回收得到乙酸铯水溶液，其中又含有原料中的铯的37％。
Claims (3)
1、从铯矾制备铯盐的方法，其特征在于：
在一单一容器中，在水存在下使铯矾与摩尔用量与铯矾中的铝的摩尔数相等的氢氧化钙、以及摩尔用量与铯矾中的铯的摩尔数相等的易溶于水的钙盐反应，反应温度为80-120℃，采用过滤或离心分离的方法分离出氢氧化铝和硫酸钙沉淀。
2、如权利要求1所述的方法，其特征在于：所述的易溶于水的钙盐为甲酸钙、乙酸钙、柠檬酸钙、氯化钙或溴化钙。
3、如权利要求1或2所述的方法，其特征在于：所述的反应是在一悬浮液中进行的，所述的悬浮液在反应开始时的稠度相当于每升水含有100～500克不溶性固体物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4313480A DE4313480C1 (de) | 1993-04-24 | 1993-04-24 | Verfahren zur Herstellung von Cäsiumsalzen aus Cäsium-Aluminium-Alaun |
| DEP4313480.7 | 1993-04-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1121705A CN1121705A (zh) | 1996-05-01 |
| CN1055677C true CN1055677C (zh) | 2000-08-23 |
Family
ID=6486296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94191890A Expired - Lifetime CN1055677C (zh) | 1993-04-24 | 1994-04-19 | 从铯矾制备铯盐的方法 |
Country Status (22)
| Country | Link |
|---|---|
| US (1) | US5605669A (zh) |
| EP (1) | EP0695286B1 (zh) |
| JP (1) | JP4079991B2 (zh) |
| KR (1) | KR100303251B1 (zh) |
| CN (1) | CN1055677C (zh) |
| AT (1) | ATE161818T1 (zh) |
| AU (1) | AU679528B2 (zh) |
| BR (1) | BR9406214A (zh) |
| CA (1) | CA2161245C (zh) |
| CZ (1) | CZ287380B6 (zh) |
| DE (2) | DE4313480C1 (zh) |
| DK (1) | DK0695286T3 (zh) |
| FI (1) | FI112204B (zh) |
| HU (1) | HU214206B (zh) |
| LV (1) | LV11540B (zh) |
| NO (1) | NO303984B1 (zh) |
| PL (1) | PL177619B1 (zh) |
| RO (1) | RO113983B1 (zh) |
| SK (1) | SK280404B6 (zh) |
| WO (1) | WO1994025422A1 (zh) |
| ZA (1) | ZA942813B (zh) |
| ZW (1) | ZW4994A1 (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6015535A (en) * | 1995-04-06 | 2000-01-18 | Cabot Corporation | Process for producing purified cesium compound from cesium alum |
| CA2217343C (en) * | 1995-04-06 | 2007-11-13 | Cabot Corporation | Process for the production of cesium compounds |
| US6652820B2 (en) | 2001-04-02 | 2003-11-25 | Cabot Corporation | Methods of making cesium salts and other alkali metal salts |
| JP5424562B2 (ja) * | 2005-01-27 | 2014-02-26 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | 水酸化セシウム溶液の製造法 |
| US7759273B2 (en) * | 2005-04-20 | 2010-07-20 | Cabot Corporation | Methods of forming an alkali metal salt |
| CN110256232B (zh) * | 2019-06-28 | 2022-05-03 | 百杰瑞(荆门)新材料有限公司 | 一种甲酸铯生产方法 |
| CN110172575B (zh) * | 2019-07-05 | 2021-03-05 | 新疆有色金属研究所 | 一种铯矾原料的处理方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1253252B (de) * | 1963-03-01 | 1967-11-02 | Atomic Energy Commission | Verfahren zum Abtrennen von radioaktivem Caesium aus waessrigen Loesungen |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2481455A (en) * | 1948-06-01 | 1949-09-06 | Dow Chemical Co | Cesium bromide separation |
| GB949483A (en) * | 1961-05-25 | 1964-02-12 | Atomic Energy Authority Uk | Improvements in or relating to the recovery of caesium |
| US3207571A (en) * | 1962-04-09 | 1965-09-21 | San Antonio Chemicals Inc | Process for preparing cesium compounds from cesium alum |
| US3130010A (en) * | 1962-12-04 | 1964-04-21 | Dow Chemical Co | Process for production of high purity cesium metal and cesium compounds |
| US3489509A (en) * | 1967-05-18 | 1970-01-13 | Kewanee Oil Co | Process for recovery of cesium compounds of high purity |
-
1993
- 1993-04-24 DE DE4313480A patent/DE4313480C1/de not_active Expired - Lifetime
-
1994
- 1994-04-19 JP JP52382394A patent/JP4079991B2/ja not_active Expired - Lifetime
- 1994-04-19 AU AU66792/94A patent/AU679528B2/en not_active Expired
- 1994-04-19 CZ CZ19952737A patent/CZ287380B6/cs not_active IP Right Cessation
- 1994-04-19 KR KR1019950704634A patent/KR100303251B1/ko not_active IP Right Cessation
- 1994-04-19 DK DK94914402.6T patent/DK0695286T3/da active
- 1994-04-19 DE DE59404963T patent/DE59404963D1/de not_active Expired - Lifetime
- 1994-04-19 US US08/537,927 patent/US5605669A/en not_active Expired - Lifetime
- 1994-04-19 CA CA002161245A patent/CA2161245C/en not_active Expired - Lifetime
- 1994-04-19 RO RO95-01847A patent/RO113983B1/ro unknown
- 1994-04-19 WO PCT/EP1994/001202 patent/WO1994025422A1/de active IP Right Grant
- 1994-04-19 ZW ZW4994A patent/ZW4994A1/xx unknown
- 1994-04-19 BR BR9406214A patent/BR9406214A/pt not_active IP Right Cessation
- 1994-04-19 HU HU9503041A patent/HU214206B/hu not_active IP Right Cessation
- 1994-04-19 SK SK1311-95A patent/SK280404B6/sk unknown
- 1994-04-19 PL PL94311231A patent/PL177619B1/pl unknown
- 1994-04-19 EP EP94914402A patent/EP0695286B1/de not_active Expired - Lifetime
- 1994-04-19 AT AT94914402T patent/ATE161818T1/de not_active IP Right Cessation
- 1994-04-19 CN CN94191890A patent/CN1055677C/zh not_active Expired - Lifetime
- 1994-04-22 ZA ZA942813A patent/ZA942813B/xx unknown
-
1995
- 1995-10-17 NO NO954134A patent/NO303984B1/no not_active IP Right Cessation
- 1995-10-23 FI FI955049A patent/FI112204B/fi not_active IP Right Cessation
- 1995-10-24 LV LVP-95-321A patent/LV11540B/lv unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1253252B (de) * | 1963-03-01 | 1967-11-02 | Atomic Energy Commission | Verfahren zum Abtrennen von radioaktivem Caesium aus waessrigen Loesungen |
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