CN1100722C - Process for precipitating B and Li in bittern at same time - Google Patents
Process for precipitating B and Li in bittern at same time Download PDFInfo
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- CN1100722C CN1100722C CN98119028A CN98119028A CN1100722C CN 1100722 C CN1100722 C CN 1100722C CN 98119028 A CN98119028 A CN 98119028A CN 98119028 A CN98119028 A CN 98119028A CN 1100722 C CN1100722 C CN 1100722C
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Abstract
The present invention belongs to the technical field of salinization industry, particularly to a method for extracting boron and lithium from brine. The method for extracting boron and lithium from brine has the technological flow of primary freezing, halogen mixing evaporation, primary evaporation, secondary freezing, secondary evaporation and boron and lithium precipitation. The method for extracting boron and lithium from brine has the technological conditions that the freezing temperature of the primary freezing and the secondary freezing is from 0 to 25 DEG C, and halogen mixing ration(volume ratio) is 1.0:0 to 1.5; potassium mixed salts and carnallite are separated out after water is removed by the primary evaporation, and the evaporation is stopped until bischofite is saturated; the secondary evaporation is stopped until the weight ratio of the content of the lithium is from 0.6 to 1.0%; excessive sulphuric acid is used for precipitating the boron and the lithium. Compared with the prior art, the method has the advantages of high yield of boron and lithium, no environmental pollution, strong practicability, etc.
Description
The invention belongs to salinization industry technical field, particularly a kind of method of from bittern, extracting the boron lithium.
The boron lithium belongs to rare and dispersed element, and content is all not high in all kinds bittern.Extract the boron lithium in the bittern, the main both at home and abroad at present evaporation concentration that adopts, make the boron lithium reach finite concentration after, extract boron with the hcl acidifying method, put forward the method that mother liquor behind the boron is carried lithium again.Adopt this method when sodium, potassium major part are separated out the high sulfate radical system of later high magnesium, though boron is not separated out with solid phase, lithium is then separated out simultaneously and is lost in the solid phase with sulfuric acid monohydrate lithium form and epsom salt, thereby has reduced the rate of recovery of lithium.The salt acid system is carried boron, and the hydrochloric acid consumption is big, salt acid value height, production cost height.
The objective of the invention is to design a kind of new boron lithium extracting method, can overcome the defective that existing method exists, it has boron lithium rate of recovery height, the advantage that production cost is low.
Technical scheme of the present invention: (one) technical process is: once freezing, convert the halogen evaporation, single vaporization, secondary is freezing, double evaporation-cooling, the technological process of precipitation boron lithium, (2) processing condition are: the freezing temp of a freezing process is 0～-25 ℃, convert the former halogen of halogen evaporization process: the halogen of converting of magnesium chloride saturated liquid is 1.0 than (volume ratio): 0-1.5, former halogen is for removing saltcake, bittern after the epsom salt, converting halogen evaporization process evaporation dewaters and separates out halite, evaporate to saturated the stopping of potassium, the single vaporization operation dewaters and separates out the potassium mixed salt, carnallitite, evaporate to saturated the stopping of bischofite, secondary freezing process freezing temp is 0～-25 ℃, separate out epsom salt, the double evaporation-cooling operation dewaters and separates out bischofite, when being 0.6～1.0% (weight ratio), lithium content stops evaporation, precipitation boron lithium operation precipitates the boron lithium with excess sulfuric acid, and pH value is 2-0.Once freezing is to be used to carry the salt lake brine of boron lithium, and sea water bittern or well halogen carry out the freezing saltcake of removing under the natural temperature in the winter time, and the process of epsom salt (7H2OMgSO4), freezing temp are 0～-25 ℃.Convert halogen evaporation and be the bittern of removing after saltcake, the epsom salt is converted people's magnesium chloride saturated solution, evaporation dewaters and separates out the process of halite (major ingredient is NaCl), converting the halogen ratio is 1.0: 0-1.5, that is to say as there not being the magnesium chloride saturated solution then can not convert halogen, direct evaporation, the control terminal point of converting the halogen evaporization process is that potassium is saturated, and promptly potassium can not be separated out to good with solid form.The single vaporization operation can adopt the means of salt pan spontaneous evaporation or heating forced evaporation to dewater and separate out the potassium mixed salt, and major ingredient such as Repone K, carnallitite, sal epsom, sodium-chlor are arranged in the potassium mixed salt, is that magnesium chloride then stops evaporation when saturated when being evaporated to bischofite.The secondary freezing process also is to utilize the winter natural temperature will go up an operation and remove the operation that bittern behind the potassium mixed salt carries out naturally frozen, separates out epsom salt in this operation.The bittern of separating out after the epsom salt then carries out double evaporation-cooling, the means of double evaporation-cooling also available salt pan spontaneous evaporation or heating forced evaporation, anhydrate in this operation and separate out chloromagnesite, along with water evaporation and bischofite are separated out, then the concentration of boron lithium further improves in the bittern, when lithium concentration rises to the 0.6-1.0% left and right sides in bittern, then stop evaporation.Remove bittern behind the bischofite and add excessive sulfuric acid and precipitate the boron lithium, bittern adds the precipitation that boron and sulfuric acid behind the sulfuric acid generate boric acid, the precipitation of lithium and sulfuric acid generation Lithium Sulphate, and it is more complete that excessive sulfuric acid then can make the boron lithium precipitate.The used sulfuric acid concentration of this operation is high more good more, preferably adopts 98% the vitriol oil, and the pH value is to begin precipitation at 2 o'clock, near 0 o'clock precipitation fully.Boric acid behind the dehalogenation and Lithium Sulphate solid are the intermediates of boracic lithium, and this intermediates mesoboric acid content is about about 30-45%, and the content of Lithium Sulphate is about about 8-14%, and these intermediates can be produced plinth acid and its lithium product through other operation again.Lithium content is about about 0.3% in the bittern after the dehydration, this bittern again and carry the former halogen of lithium and mix and reclaim, to improve lithium, the boron rate of recovery.Twice of this process using is freezing, operations such as twice evaporation are cores of the present invention, twice freezing is to remove sulfate ions a large amount of in the bittern, can effectively prevent bittern lithium and sulfate ion in concentration process to separate out with the solid form of Lithium Sulphate, twice evaporation then is to carry out bittern to concentrate the process of potassium mixed salt and bischofite of separating out.Adding people's sulfuric acid, the boron lithium is precipitated simultaneously also is technological core of the present invention.The present invention is suitable for sulfate type or chloride type bittern.
The present invention has removed a large amount of sulfate ions in the bittern because the employing secondary is freezing, thereby lithium can not separated out with the Lithium Sulphate solid in evaporating concentration process, thereby has effectively improved the yield of lithium.The boron lithium is carried in the bittern circulation of carrying in addition behind the boron lithium, and the yield of its boron lithium is higher, and non-environmental-pollution, and the solids that evaporation is separated out can fully utilize.Especially utilize this method winter temperature low, the summer climate drying is carried out the freezing and method of evaporating in secondary salt pan, and better practicality and economic benefit are arranged.But this technology need utilize winter freezing, so the production cycle is longer.
Accompanying drawing is a process flow diagram of the present invention.
Embodiment one: get 800 kilograms of certain salt lake vitriolate type bitterns in spring, according to this technical process test, one time freezing temp is about-10 ℃, remove the mother liquor behind the solid after freezing, old halogen-magnesium chloride saturated liquid with 300 kilograms is converted halogen, revaporization when saturated, is removed the halite solid to potassium, and bittern carries out single vaporization, the evaporation open-air evaporation of part is in may anhydrated, the potassium mixed salt is some, freezing then in the winter time November of secondary is about freezing temp-15 ℃, double evaporation-cooling then evaporates in the open in the March, it is 98% the excessive vitriol oil that precipitation boron lithium adds people's concentration, and pH value is 0.2 to stop to add sulfuric acid, and the post precipitation dehalogenation can get some boric acid, the Lithium Sulphate intermediates.
Embodiment two: get 1000 kilograms in chloride type bittern after the salt manufacturing of Tianjin saltworks, once freezing be October at the bottom of, freezing temp is about 0～-5 ℃, it converts the halogen ratio is 1.0: 0, single vaporization operation and double evaporation-cooling operation adopt the heating forced evaporation, and secondary is freezing to be freezing outside the bottom compartment in December, about-12 ℃～-13 ℃ approximately of temperature, the sulfuric acid concentration of precipitation boron lithium operation is 50%, and pH value is controlled to 0.1 and is advisable.
Claims (2)
1. precipitate the method for boron lithium in the bittern simultaneously, it is characterized in that technical process is for once freezing, convert the halogen evaporation, single vaporization, secondary is freezing, double evaporation-cooling, the technological process of precipitation boron lithium, processing condition are once freezing and the freezing temp secondary freezing process is 0～-25 ℃, convert the former halogen of halogen evaporization process: the halogen specific volume ratio of converting of magnesium chloride saturated liquid is 1.0: 0～1.5, former halogen is for removing saltcake, bittern after the epsom salt, converting the halogen evaporization process dewaters and separates out halite, evaporate to saturated the stopping of potassium, the single vaporization operation dewaters and separates out the potassium mixed salt, carnallitite, evaporate to saturated the stopping of bischofite, the double evaporation-cooling operation is separated out bischofite, stop evaporation during for 0.6-1.0% to the lithium content weight ratio, precipitation boron lithium is with excess sulfuric acid precipitation boron lithium, and pH value is 2-0.
2, method according to claim 1, the sulfuric acid that it is characterized in that precipitating the boron lithium is 98% the vitriol oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98119028A CN1100722C (en) | 1998-09-25 | 1998-09-25 | Process for precipitating B and Li in bittern at same time |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98119028A CN1100722C (en) | 1998-09-25 | 1998-09-25 | Process for precipitating B and Li in bittern at same time |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1249272A CN1249272A (en) | 2000-04-05 |
| CN1100722C true CN1100722C (en) | 2003-02-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98119028A Expired - Fee Related CN1100722C (en) | 1998-09-25 | 1998-09-25 | Process for precipitating B and Li in bittern at same time |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408705C (en) * | 2003-04-30 | 2008-08-06 | 中国科学院青海盐湖研究所 | Nano-filtration method for separating magnesium and enriching lithium from salt lake brine |
| AU2011236094B2 (en) * | 2011-01-20 | 2012-11-29 | Rockwood Lithium Inc. | Production of high purity lithium compounds directly from lithium containing brines |
| CN102910652A (en) * | 2012-10-18 | 2013-02-06 | 中国科学院青海盐湖研究所 | Clean production process of plateau sulfate type boron-lithium salt lake brine |
| CN105502440B (en) * | 2015-12-04 | 2019-03-26 | 中国科学院青海盐湖研究所 | The rough refining methd of sulfuric acid lithium salts |
| CN109019641B (en) * | 2018-10-12 | 2020-12-11 | 中国科学院青海盐湖研究所 | Method for separating magnesium and lithium and enriching lithium from sodium sulfate subtype salt lake brine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS565319A (en) * | 1979-06-26 | 1981-01-20 | Agency Of Ind Science & Technol | Process for recovering lithium from bittern |
| CN1014349B (en) * | 1989-04-07 | 1991-10-16 | 范朝来 | Screw driving mechanism |
| CN1141263A (en) * | 1995-07-18 | 1997-01-29 | 塔里木科学采矿和石油勘探公司 | Process for recovery of lithium and other metals and salts from brines by fractional crystallization using solar energy |
-
1998
- 1998-09-25 CN CN98119028A patent/CN1100722C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS565319A (en) * | 1979-06-26 | 1981-01-20 | Agency Of Ind Science & Technol | Process for recovering lithium from bittern |
| CN1014349B (en) * | 1989-04-07 | 1991-10-16 | 范朝来 | Screw driving mechanism |
| CN1141263A (en) * | 1995-07-18 | 1997-01-29 | 塔里木科学采矿和石油勘探公司 | Process for recovery of lithium and other metals and salts from brines by fractional crystallization using solar energy |
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| CN1249272A (en) | 2000-04-05 |
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