CN102557085A - Method for producing cesium salt and rubidium salt based on zero discharge and continuous extraction - Google Patents
Method for producing cesium salt and rubidium salt based on zero discharge and continuous extraction Download PDFInfo
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Abstract
The invention relates to a method for producing cesium salt and rubidium salt based on zero discharge and continuous extraction, which comprises the following steps: pretreating ores containing cesium and rubidium in a container by a leaching process, adding alkali liquor into the obtained liquid to regulate the pH value to 11-13, adding an extractant, carrying out back washing on the supernatant solution containing caesium ions after extraction to obtain the cesium salt solution of the corresponding acid, and carrying out centrifugal drying to prepare the cesium salt; and sending the understratum solution containing rubidium ions after extraction into a second continuous extraction box for extraction, carrying out back washing on the supernatant solution containing rubidium ions after extraction to obtain a rubidium salt solution of the corresponding acid, carrying out centrifugal drying to obtain the rubidium salt, and putting the etching solutions generated in the steps into raw material containers for use. The invention enhances the production efficiency, and implements the uninterrupted and continuous production of cesium salt and rubidium salt extraction; the discharge of three wastes is almost zero; and the filter cake crystal in the raw material feed stage can be recrystallized to extract the high-purity sodium salt.
Description
Technical field:
The present invention relates to the working method of a kind of cesium salt and rubidium salt, more specifically to a kind of method of producing cesium salt and rubidium salt based on zero release, continuous extraction.
Background technology:
In the prior art; The method of producing cesium salt has two kinds: a kind of is alkaline process production, and the weak point of alkaline process production at present is: the technical requirements to equipment is too high, and temperature of reaction is too high and the time is long; Temperature reaches 900 ℃; The energy consumption of thereupon bringing is also high, and ultimate demand uses chemical method to make finished product, and the pollution of residue feed liquid is comparatively serious; What another weak point was that traditional alkaline process production carries out is article one stills; The regeneration product need feed intake again; Raw materials cost strengthens; Waste liquid after produce finishing because impurity is too high can't be recycled, can only entrust the specialized company of qualification to handle with waste residue, and therefore the cost of the transportation and three wastes processing raises once more.Another kind is acid system production, and the weak point of acid system production at present is: oversize from the process that is dosed into production, and boil and reach 16 hours; Have a strong impact on the cycle of production, improve cost of labor, when removal of impurities, need add barium hydroxide; This type of barium salt has toxicity; Security can't be guaranteed, and need constantly add the maintenance that water carries out volume in process of production, and operability is poor; Therefore this method is prone to cause that concentration is low excessively, poor stability, production cycle be long, the too high defective of cost that the three wastes are handled.Relevant report is not seen in preparation as for rubidium salt in the market as yet, and only is the mixed solution of the saturated solution of caesium and ribidium salt solution or caesium and ribidium salt solution and basic metal or alkaline earth salt.
Summary of the invention:
The objective of the invention is to be directed against the prior art weak point and a kind of low power consuming, low cost, work simplification, the method based on zero release, continuous extraction production cesium salt and rubidium salt safe no hidden danger, that production efficiency is high are provided.
Another object of the present invention provides a kind of method of separating cesium salt and rubidium salt from caesium and ribidium salt solution or caesium and the ribidium salt solution and the mixed solution of the saturated solution of basic metal or alkaline earth salt.
The 3rd purpose of the present invention provides a kind of working method of producing rubidium salt.
The 4th purpose of the present invention provides a kind of method of extracting sodium salt in caesium, the rubidium salt process of producing.
The objective of the invention is to realize through following measure: a kind of method of producing cesium salt and rubidium salt based on zero release, continuous extraction is characterized in that step is following:
Step 1, in container, adopt lixiviation process that the ore that contains caesium, rubidium is carried out pre-treatment; Temperature is 85 ℃～105 ℃; Soak time 4～6 hours adds alkali lye and regulates pH value to 11～13 in gained liquid, cross through decrease temperature crystalline to filter again: contain the stoste of cesium salt, rubidium salt and contain the crystallization of sodium salt;
Step 2, the stoste that the step 1 gained is contained cesium salt, rubidium salt are injected the continuous extraction case; Adding extraction agent T-BAMBP extracts; Said extraction agent add-on: concentration is that the ratio of extraction agent and the stoste weight of 1mol/L is 4: 3; The solution that leach liquor upper strata after the extraction extraction contains cesium ion gets into the back extraction container, and the solution that the leach liquor lower floor after the extraction extraction contains rubidium ion gets into the second continuous extraction case;
Step 3, the solution that contains cesium ion that gets in the back extraction container is carried out back extraction, add acid solution and high purity water and get: callable extraction liquid and the cesiated salt solution that contains respective acids; Said cesiated salt solution is accomplished the cesium salt preparation through centrifugal, dry again, and the centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns extraction process and recycles;
Step 4, the solution that contains rubidium ion that gets into the second continuous extraction case is added extraction agent T-BAMBP extract; Said extraction agent add-on: concentration be 1mol/L extraction agent with by the collection solution weight ratio be 4: 3; The leach liquor upper solution of extracting after extracting gets into the second back extraction container, and the leach liquor lower floor liquid that extracts after extracting returns in the container of step 1;
Step 5, the leach liquor upper solution that gets into after the extraction in the second back extraction container is carried out back extraction; Adding acid solution and high purity water gets: callable extraction liquid and the ribidium salt solution that contains respective acids; Said rubidium salt holds liquid again through the preparation of centrifugal, dry completion rubidium salt; The centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns extraction process and recycles.
The alkali lye that adds in the said step 1 is sodium hydroxide or quicklime or calcium hydroxide or yellow soda ash.
Acid solution that adds in the said step 3 and high purity water; Said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate; The purity of said acid solution is >=99%; Add-on is 140g～160g/L, and said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight.
Acid solution and high purity water that said step 5 adds; Said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate; The purity of said acid solution is >=99%; Add-on is 140g～160g/L, and said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight.
A kind of from caesium and ribidium salt solution or caesium and ribidium salt solution and the method that the mixed solution of the saturated solution of basic metal or alkaline earth salt separates cesium salt and rubidium salt, it is characterized in that step is following:
Step 1, with the mixing solutions of the saturated solution that contains caesium and ribidium salt solution or caesium and ribidium salt solution and basic metal or alkaline earth salt in the container; Regulate pH between 11～13; Inject the continuous extraction case; Adding extraction agent T-BAMBP extracts; Said extraction agent add-on: concentration is the extraction agent of 1mol/L and be 4: 3 by the ratio of weight of collection solution, extracts the solution that leach liquor upper strata after the extraction contains cesium ion and gets into the back extraction container, extracts the solution that leach liquor lower floor after the extraction contains rubidium ion and gets into the second continuous extraction case;
Step 2, the solution that contains cesium ion that gets in the back extraction container is carried out back extraction; Adding acid solution and high purity water gets: callable extraction liquid and the cesiated salt solution that contains respective acids, and said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate, the purity of said acid solution is >=99%; Add-on is 140g～160g/L; Said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight, and said cesiated salt solution is again through the preparation of centrifugal, dry completion cesium salt; The centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns extraction process and recycles;
Step 3, the solution that contains rubidium ion that gets into the second continuous extraction case is added extraction agent T-BAMBP extract; Said extraction agent add-on: concentration is the extraction agent of 1mol/L and be 4: 3 by the ratio of weight of collection solution; The solution that leach liquor upper strata after the extraction extraction contains rubidium ion gets into the second back extraction container, and the leach liquor lower floor liquid that extracts after extracting returns in the container of step 1;
Step 4, the solution that contains rubidium ion that gets in the second back extraction container is carried out back extraction; Adding acid solution and high purity water gets: callable extraction liquid and the ribidium salt solution that contains respective acids, and said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate, the purity of said acid solution is >=99%; Add-on is 140g～160g/L; Said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight, and said ribidium salt solution is again through the preparation of centrifugal, dry completion rubidium salt; The centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns extraction process and recycles.
A kind of working method of producing rubidium salt is characterized in that step is following:
Collect the solution after the leaching of ore of solution that leach liquor lower floor behind the caesium solution extraction contains rubidium ion or commercial rubidium in step 1, the container or contain more than one the mixing solutions of lean solution or aforementioned solution of rubidium element; Regulating pH sends in the continuous extraction case after between 11～13; Adding extraction agent T-BAMBP extracts; Said extraction agent add-on: concentration is the extraction agent of 1mol/L and be 4: 3 by the ratio of weight of collection solution; The solution that leach liquor upper strata after the extraction extraction contains rubidium ion gets into the back extraction container, and the leach liquor lower floor liquid that extracts after extracting returns in the container;
Step 2, the solution that contains rubidium ion that gets in the back extraction container is carried out back extraction; Adding an amount of acid solution and high purity water gets: callable extraction liquid and the ribidium salt solution that contains respective acids, and said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate, the purity of said acid solution is >=99%; Add-on is 140g～160g/L; Said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight, and said ribidium salt solution is again through the preparation of centrifugal, dry completion rubidium salt; The centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns the step 1 extraction process and recycles.
A kind of method of extracting sodium salt in caesium, the rubidium salt process of producing is characterized in that step is following:
Step 1, in container, adopt lixiviation process that the ore that is rich in caesium, rubidium is carried out pre-treatment, leach at gained and add alkali lye in the stoste and regulate pH value to 11～13, the process leaching contains the crystallization of sodium salt;
Step 2, the filter residue that contains sodium salt is washed, behind the decrease temperature crystalline high-purity moisture sodium salt.
Compared with prior art, the method based on zero release, continuous extraction production cesium salt and the production of rubidium salt that the present invention proposes has following advantage: 1) improved production efficiency, realized the uninterrupted and continuity that cesium salt, rubidium salt extraction are produced; 2) three waste discharge is almost nil; The three wastes that the present invention produced all use in the continual extraction process in the continuous extraction case of circulation; A part is used as the mother liquor of rubidium salt, and another part finishes the back and continues use in putting into production again as the mother liquor of cesium salt producing; 3) throwing in the filter cake crystallisate in stage at raw material can utilize recrystallization to extract highly purified sodium salt.Production technique of the present invention has solved the problem of environmental improvement fully; On the production cycle, because be that the continuous uninterrupted extraction is produced, the therefore energy-saving and cost-reducing emphasis that becomes; The input ratio traditional technology of present device few 2/3rds; The use of energy consumption reduces 1/3rd, is favourable for reducing enterprise cost, and the quality of product improves a rank than traditional technology.
Description of drawings:
Fig. 1 is the process flow sheet of one embodiment of the invention.
Embodiment:
Below in conjunction with accompanying drawing embodiment is elaborated:
Fig. 1 is the process flow sheet of one embodiment of the invention.Among the figure, a kind of method of producing cesium salt and rubidium salt based on zero release, continuous extraction, step is following:
Step 1, in container, adopt lixiviation process that the ore that contains caesium, rubidium is carried out pre-treatment; Temperature is 85 ℃～105 ℃; Soak time 4～6 hours adds alkali lye and regulates pH value to 11～13 in gained liquid, cross through decrease temperature crystalline to filter again: contain the stoste of cesium salt, rubidium salt and contain the crystallization of sodium salt.The solution that adopts sulfuric acid to adopt in the present embodiment as lixiviation process, or also can be and require the to produce corresponding acid solution of cesium salt.
Step 2, the stoste that the step 1 gained is contained cesium salt, rubidium salt are injected the continuous extraction case; Adding extraction agent T-BAMBP extracts; Extraction agent T-BAMBP is commercial, the Chinese 4-tertiary butyl-2-(α-Jia Jibianji) phenol by name, English for 4-tert-butyl-2-(α-methyl benzyl) phenol, its molecular formula be C
18H
22O, molecular weight: 254, pH: slant acidity, below used extraction agent T-BAMBP be identical product.Said extraction agent add-on: concentration is that the ratio of extraction agent and the stoste weight of 1mol/L is 4: 3; The solution that leach liquor upper strata after the extraction extraction contains cesium ion gets into the back extraction container, and the solution that the leach liquor lower floor after the extraction extraction contains rubidium ion gets into the second continuous extraction case.
Step 3, the solution that contains cesium ion that gets in the back extraction container is carried out back extraction, add acid solution and high purity water and get: callable extraction liquid and the cesiated salt solution that contains respective acids; Said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate, and the selection principle of acid solution is relevant with the salt of producing which kind of type, produces cesium sulfate in this instance and then adopts cesium sulfate; The purity of said sulfuric acid liquid is >=99%, and add-on is 140g～160g/L, and said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight; Said cesium sulfate salts solution is accomplished the preparation of sulfuric acid cesium salt through centrifugal, dry again, and the centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns extraction process and recycles;
Step 4, the solution that contains rubidium ion that gets into the second continuous extraction case is added extraction agent T-BAMBP extract; Said extraction agent add-on: concentration is the extraction agent of 1mol/L and be 4: 3 by the ratio of weight of collection solution; The leach liquor upper solution of extracting after extracting gets into the second back extraction container, and the leach liquor lower floor liquid that extracts after extracting returns in the container of step 1;
Step 5, the leach liquor upper solution that gets in the second back extraction container is carried out back extraction, add sulfuric acid liquid and high purity water and get: callable extraction liquid and rubidiurn sulfate salts solution; The purity of said sulfuric acid liquid is >=99%, and add-on is 140g～160g/L, and said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight; Said rubidiurn sulfate salts solution is accomplished the preparation of rubidiurn sulfate salt through centrifugal, dry again, and the centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns extraction process and recycles.
A kind of method of separating cesium salt and rubidium salt from caesium and ribidium salt solution or caesium and the ribidium salt solution and the mixed solution of the saturated solution of basic metal or alkaline earth salt; Step is with the said step of aforementioned method; Different places are: stoste can be the stoste that contains cesium salt, rubidium salt of gained when adopting lixiviation process to carry out pre-treatment to the ore that is rich in caesium, rubidium; It also can be the mixed solution that contains the saturated solution of caesium and ribidium salt solution or caesium and ribidium salt solution and basic metal or alkaline earth salt; The pH of adjustment solution is to 11～13 before extraction, and the step with the method for producing cesium salt and rubidium salt based on zero release, continuous extraction is identical fully thereafter.
A kind of working method of producing rubidium salt, step is following:
Solution after step 1, the ore of collecting solution that leach liquor lower floor behind the caesium solution extraction contains rubidium ion or commercial rubidium leach or contain the lean solution of rubidium element; Or more than one mixing solutions of aforementioned solution; Regulating pH value to 11～13 sends in the continuous extraction case; Adding extraction agent T-BAMBP extracts; Said extraction agent add-on: concentration is the extraction agent of 1mol/L and be 4: 3 by the ratio of collection solution weight, extracts the solution that leach liquor upper strata after the extraction contains rubidium ion and gets into the back extraction container, and the leach liquor lower floor liquid that extracts after the extraction returns in the container;
Step 2, the solution that contains rubidium ion that gets in the back extraction container is carried out back extraction; Adding sulfuric acid liquid and high purity water gets: callable extraction liquid and rubidiurn sulfate salts solution; The purity of said sulfuric acid liquid is >=99%; Add-on is 140g～160g/L, and said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight; Said rubidiurn sulfate salts solution is accomplished the preparation of rubidiurn sulfate salt through centrifugal, dry again, and the centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns the step 1 extraction process and recycles.
A kind of method of extracting sodium salt in caesium, the rubidium salt process of producing, step is following:
Step 1, in container, adopt lixiviation process that the ore that contains caesium, rubidium is carried out pre-treatment, temperature is 85 ℃～105 ℃, and soak time 4～6 hours leaches at gained and to add alkali lye in the stoste and regulate pH value to 11～13, crosses through decrease temperature crystalline and filters the crystallization that contains sodium salt;
Step 2, the crystallization that contains sodium salt is washed, behind the decrease temperature crystalline high-purity moisture sodium salt.
Principle of work of the present invention is following:
The present invention regulates the pH value to the leach liquor under acidic conditions and extracts through the ore that contains caesium, rubidium is carried out pre-treatment, because caesium and rubidium are the elements of same main group; Extraction all is the principle of polarity similar compatibility; But the polarity of caesium and rubidium and molecular weight are different and since caesium be arranged in rubidium above, so the metallicity of caesium is weaker than rubidium; So caesium combines prior to extraction agent, only react there not being under the situation of caesium rubidium just might combine with extraction agent.Based on this principle, in the solution that contains caesium, rubidium, at first form the compound of caesium behind the adding extraction agent T-BAMBP, then extraction liquid is carried out back extraction and can obtain the cesium salt of acid accordingly with corresponding acid; Extraction waste liquid later gets in the continuous multistage cycling extraction case of another one again; Can in solution, not have under the situation of caesium gradually to come thereby add rubidium that efficient extraction agent T-BAMBP contains once more in waste liquid yet, thereby send into corresponding acid once more, then can extract the rubidium salt of corresponding acid with the isolated in form of the mixture of rubidium and metals ion; This measure just can realize that the uninterrupted continuously of cesium salt and rubidium salt produces; Extracted waste liquid after the rubidium salt and can squeeze into the multistage cycling extraction case of the first step once more and go into operation as the mother liquor of producing next time, because the metals ion of the inside has been extracted completion, this measure realizes the not discharge cycle utilization of the three wastes; Reduce the improvement pressure of environment; In the process that feeds intake of raw material, need once filter leach liquor, crystalline material can appear in filtration procedure; By traditional technology with this crystalline solid as waste disposal; Nowadays its recovery can be gone out highly purified aqueous sulfuric acid sodium by recrystallization, this measure reduces the improvement pressure of environment once more, and the value of good use waste material is arranged.
Further explain below with embodiment:
Embodiment 1
Fs is produced cesium salt: the ore that in container, will contain caesium, rubidium leaches; 85 ℃ of temperature of reactor, soak time 6 hours, decrease temperature crystalline; Leach adding alkali lye sodium hydroxide adjusting pH value to 13 in the liquid at gained, cross and filter stoste that contains cesium salt, rubidium salt and the crystallization that contains sodium salt; Afterwards, stoste is added extraction agent T-BAMBP extract, extractant concentration is 1mol/L; The weight ratio of extraction agent and stoste is 4: 3, after the layering subnatant of raffinate is squeezed in the second multistage cycling extraction case to add extraction agent T-BAMBP and extract, and extractant concentration is: 1mol/L; Extraction agent is 4: 3 with the ratio of the weight of stoste, continue after in the back extraction container, to add purity be >=99% carbonic acid gas 150g/L and the entering of the high purity water more than 15 Ω strip stages, the amount of high purity water is 1/6 of a stripping workshop weight; Get cesium carbonate solution; Be 1100r/m whiz 30min through rotating speed again, 400 ℃ dry solid-state cesium carbonate
The high-purity moisture sodium salt that subordinate phase recovery filtration stage produces: the filtration stage after containing caesium, the leaching of rubidium ore, gained is contained the sodium salt crystal washing, get high-purity moisture sodium salt behind the cooling recrystallization.
Phase III utilizes the raffinate of fs reclaim to produce rubidium salt: feed liquid with the fs after centrifugal and the waste liquid unification in the extraction process are recovered in the material container; Be that 1/6 high purity water of solution weight gets into strip stages with adding purity in the upper solution of the extraction that extracts in another multistage cycling extraction case for >=99% carbonic acid gas 150g/L and the amount more than 15 Ω afterwards; Get rubidium carbonate solution; Be 1000r/m whiz 25min through rotating speed again; 350 ℃ dry the solid carbonic acid rubidium, and waste liquid unification in feed liquid after centrifugal and the extraction process is recovered in the multistage cycling extraction case, use as the mother liquor of next extractive reaction.
Stage: the waste liquid that utilizes all generations is as recycling and continual production in the mother liquor input material container that extracts next time.
Its technical indicator is listed in the following table (1).
Embodiment 2
Fs: the ore that in container, will contain caesium, rubidium leaches, 85 ℃ of temperature of reactor, soak time 6 hours; Regulate pH value to 12, will contain the crystalline feed liquid behind the decrease temperature crystalline and filter, cross and filter stoste that contains cesium salt, rubidium salt and the crystallization that contains sodium salt; Stoste is added extraction agent T-BAMBP extract, said extractant concentration is 1mol/L, and the weight ratio of extraction agent and stoste is 4: 3; After the layering lower floor's solution behind the single extraction squeezed in the second multistage cycling extraction case and add extraction agent T-BAMBP and extract, said extractant concentration is 1mol/L, and the weight ratio of extraction agent and stoste is 4: 3; Continue after in the back extraction container, to add purity be >=99% carbonic acid gas 145g/L; And the above high purity water entering strip stages of 15 Ω, the amount of high purity water is 1/6 of a solution weight, gets cesium carbonate solution; Be 1100r/m whiz 30min through rotating speed again, 400 ℃ dry solid-state cesium carbonate.
Subordinate phase reclaims the high-purity moisture sodium salt that filtration stage produces: the filtration stage after containing caesium, the leaching of rubidium ore, gained is contained the sodium crystallizing and washing, and get high-purity moisture sodium salt behind the cooling recrystallization.
Phase III utilizes the raffinate of fs reclaim to produce rubidium salt: solution with the fs after centrifugal and the waste liquid unification in the extraction process are recovered in the material container; Afterwards with add in the raffinate that extracts in the second multistage cycling extraction case purity >=99% carbonic acid gas 145g/L and the amount more than 15 Ω are that 1/6 high purity water of stripping workshop weight gets into strip stages; Get rubidium carbonate solution; Be 1000r/m whiz 25min through rotating speed again; 350 ℃ dry the solid carbonic acid rubidium, and waste liquid unification in feed liquid after centrifugal and the extraction process is recovered in the multistage cycling extraction case, use as the mother liquor of next extractive reaction.
Stage: the waste liquid that utilizes all generations is as recycling and continual production in the mother liquor input material container that extracts next time.
Its technical indicator is listed among following table the present invention (2).
Embodiment 3
Fs: the ore that in container, will contain caesium, rubidium leaches; 85 ℃ of temperature of reactor, soak time 6 hours is regulated pH value to 12 with alkali lye; To contain the crystalline feed liquid behind the decrease temperature crystalline and filter, and cross and filter stoste that contains cesium salt, rubidium salt and the crystallization that contains sodium salt.Afterwards, stoste is added extraction agent T-BAMBP extract, said extractant concentration is 1mol/L; The weight ratio of extraction agent and stoste is 4: 3, after the layering subnatant of a raffinate is squeezed in the second multistage cycling extraction case to add extraction agent T-BAMBP and extract, and said extractant concentration is 1mol/L; The weight ratio of extraction agent and stoste is 4: 3, continue after in the back extraction container, to add purity be >=99% acetate 130g/L and the entering of the high purity water more than 15 Ω strip stages, the amount of high purity water is 1/6 of a feed liquid; Get cesium acetate solution; Be 1100r/m whiz 30min through rotating speed again, 400 ℃ dry solid-state cesium acetate
Subordinate phase reclaims the high-purity moisture sodium salt that filtration stage produces: the filtration stage after containing caesium, the leaching of rubidium ore, gained is contained the sodium crystallizing and washing, and get high-purity moisture sodium salt behind the cooling recrystallization.
Phase III utilizes the raffinate of fs reclaim to produce rubidium salt: feed liquid with the fs after centrifugal and the waste liquid unification in the extraction process are recovered in the material container; Be that 1/6 high purity water of stripping workshop weight gets into strip stages with adding highly purified acetate 130g/L and the amount more than 15 Ω in the raffinate that extracts in the second multistage cycling extraction case afterwards; Get rubidium acetate solution; Be 1000r/m whiz 25min through rotating speed again; 350 ℃ dry the solid rubidium acetate, and waste liquid unification in feed liquid after centrifugal and the extraction process is recovered in the multistage cycling extraction case, use as the mother liquor of next extractive reaction.
Stage: the waste liquid that utilizes all generations is as recycling and continual production in the mother liquor input material container that extracts next time.
Embodiment 4
Fs: the ore that in container, will contain caesium, rubidium leaches, 85 ℃ of temperature of reactor, and soak time 6 hours adds alkali lye sodium hydroxide and regulates pH value to 12; To contain the crystalline feed liquid behind the decrease temperature crystalline and filter, and cross and filter stoste that contains cesium salt, rubidium salt and the crystallization that contains sodium salt.Stoste is added extraction agent T-BAMBP extract, said extractant concentration is 1mol/L, and the weight ratio of extraction agent and stoste is 4: 3; After the layering subnatant of a raffinate squeezed in the second multistage cycling extraction case and add extraction agent T-BAMBP and extract, said extractant concentration is 1mol/L, and the weight ratio of extraction agent and stoste is 4: 3; Continue after in the back extraction container, to add purity be >=99% sulfuric acid 155g/L and the entering of the high purity water more than 15 Ω strip stages; The amount of high purity water is 1/6 of a stripping workshop weight, gets cesium sulfate solution, is 1100r/m whiz 30min through rotating speed again; 400 ℃ dry solid-state cesium sulfate
Subordinate phase reclaims the high-purity moisture sodium salt that filtration stage produces: the filtration stage after containing caesium, the leaching of rubidium ore, gained is contained the sodium crystallizing and washing, and get high-purity moisture sodium salt behind the cooling recrystallization.
Phase III utilizes the raffinate of fs reclaim to produce rubidium salt: feed liquid with the fs after centrifugal and the waste liquid unification in the extraction process are recovered in the material container; Be that 1/6 high purity water of stripping workshop weight gets into strip stages with the sulfuric acid 155g/L that adds high purity >=99% in the raffinate that extracts in the second multistage cycling extraction case and the amount more than 15 Ω afterwards; Get rubidiurn sulfate solution; Be 1000r/m whiz 25min through rotating speed again; 350 ℃ dry the solid sulphuric acid rubidium, and waste liquid unification in feed liquid after centrifugal and the extraction process is recovered in the multistage cycling extraction case, use as the mother liquor of next extractive reaction.
Stage: the waste liquid that utilizes all generations is as recycling and continual production in the mother liquor input material container that extracts next time.
Preparing main quality index by preparation method of the present invention and traditional method sees the following form:
The technical indicator of high-purity moisture sodium salt:
The technical indicator of rubidium carbonate:
Economic and social benefit:
The economic construction of China at present is in the period of a transition, turns to the economized form of efficient, energy-conservation, safety, environment-friendly type from traditional industrial economy.Conventional industries economy be with expensive, promote overstocked commodities, have potential safety hazard, high energy consumption, ignore the economy of the traditional business model of environment, no technological transformation, be a kind of lossy economy.Modern economy then is to safeguard environment for human survival, Reasonable Protection resource and the energy, to be of value to the economy that HUMAN HEALTH is a characteristic, is a kind of balanced type economy.Traditional alkaline process production and acid system production are comparatively typical conventional industries economy, and traditional alkaline process production uses high heat-stable material and production cycle for a long time to become main flow, its power consumption, consuming time expensive be the bottleneck that puzzlement is produced.Technology of the present invention is to the pre-treating process of raw material, and the required equipment expense is merely 1/3rd of traditional process equipment input, aspect energy-saving and cost-reducing; Because of not adopting under 900 ℃ of high temperature calcination 6 hours, the energy of the required consumption of this technology is merely 1/3rd of traditional technology consumes energy in energy-saving and cost-reducing, in the production cycle, has avoided the poor efficiency mode of production of article one still that traditional technology adopted; Use the continuously uninterrupted efficiently mode of production instead; Thereby significantly reduced the production cycle, brought into play the multi-purpose ability of a kind of technology, used a technology can produce two kinds of products; And even more corresponding product, thereby reduce enterprise cost.Traditional acid system production is in order to obtain highly purified cesium salt or rubidium salt; In the pre-treatment of raw material, need the leaching up to 16 hours consuming time; For need adding a large amount of barium hydroxides, acid ion, metals ion in the removing solution carry out removal of impurities; In this process, can produce highly toxic substances such as barium carbonate, bring unsafe factor.Technology of the present invention need not high-purity cesium ion leach liquor, reaches 4～6 hours pH in immersion and can isolate required corresponding cesium salt at 11～13 o'clock adding extraction agents, does not therefore introduce any material that does not also produce safety hazards in the whole technology.Therefore cesium ion does not cause damage and wastes and its waste liquid can be used as down the mother liquor that secondary response feeds intake and the mother liquor of rubidium salt extraction when secondary response in the whole extraction process; So traditional technology is merely 80% and do not have waste liquid and get rid of to the leaching yield of cesium ion up to 98.5% in the leach liquor of this technology, reduces the pressure of environmental improvement.The present invention is directed to the problem that prior art exists; The preparation method who researched and developed that a kind of low power consuming, low cost, work simplification, nontoxicity intermediate product, purity are higher, cesium salt, rubidium salt and the sub product thereof of environmental protection more, the discharging of no Litter reclaims has obtained the better cesium salt of quality, rubidium salt and sub product thereof.Economic aspect has been obtained obvious improvement rebuilding traditional industry.
More than combine embodiment to be described, the foregoing description is not construed as limiting the invention, and adopts the technical scheme that form obtained that is equal to replacement or equivalent transformation in every case, all drops within protection scope of the present invention.
Claims (7)
1. method of producing cesium salt and rubidium salt based on zero release, continuous extraction is characterized in that step is following:
Step 1, in container, adopt lixiviation process that the ore that contains caesium, rubidium is carried out pre-treatment; Temperature is 85 ℃～105 ℃; Soak time 4～6 hours adds alkali lye and regulates pH value to 11～13 in gained liquid, cross through decrease temperature crystalline to filter again: contain the stoste of cesium salt, rubidium salt and contain the crystallization of sodium salt;
Step 2, the stoste that the step 1 gained is contained cesium salt, rubidium salt are injected the continuous extraction case; Adding extraction agent T-BAMBP extracts; Said extraction agent add-on: concentration is that the ratio of extraction agent and the stoste weight of 1mol/L is 4: 3; The solution that leach liquor upper strata after the extraction extraction contains cesium ion gets into the back extraction container, and the solution that the leach liquor lower floor after the extraction extraction contains rubidium ion gets into the second continuous extraction case;
Step 3, the solution that contains cesium ion that gets in the back extraction container is carried out back extraction, add acid solution and high purity water and get: callable extraction liquid and the cesiated salt solution that contains respective acids; Said cesiated salt solution is accomplished the cesium salt preparation through centrifugal, dry again, and the centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns extraction process and recycles;
Step 4, the solution that contains rubidium ion that gets into the second continuous extraction case is added extraction agent T-BAMBP extract; Said extraction agent add-on: concentration is that the ratio of extraction agent and the weight that contains rubidium ion solution of 1mol/L is 4: 3; The leach liquor upper solution of extracting after extracting gets into the second back extraction container, and the leach liquor lower floor liquid that extracts after extracting returns in the container of step 1;
Step 5, the leach liquor upper solution that gets into after the extraction in the second back extraction container is carried out back extraction; Adding acid solution and high purity water gets: callable extraction liquid and the ribidium salt solution that contains respective acids; Said ribidium salt solution is again through the preparation of centrifugal, dry completion rubidium salt; The centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns extraction process and recycles.
2. method of producing cesium salt and rubidium salt based on zero release, continuous extraction according to claim 1 is characterized in that the alkali lye that adds in the said step 1 is sodium hydroxide or quicklime or calcium hydroxide or yellow soda ash.
3. method of producing cesium salt and rubidium salt according to claim 1 and 2 based on zero release, continuous extraction; It is characterized in that, acid solution that adds in the said step 3 and high purity water, said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate; The purity of said acid solution is >=99%; Add-on is 140g～160g/L, and said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight.
4. method of producing cesium salt and rubidium salt according to claim 1 and 2 based on zero release, continuous extraction; It is characterized in that, acid solution that adds in the said step 5 and high purity water, said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate; The purity of said acid solution is >=99%; Add-on is 140g～160g/L, and said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight.
5. one kind from caesium and ribidium salt solution or caesium and ribidium salt solution and the method that the mixed solution of the saturated solution of basic metal or alkaline earth salt separates cesium salt and rubidium salt, it is characterized in that step is following:
Step 1, with the mixing solutions of the saturated solution of caesium in the container and ribidium salt solution or caesium and ribidium salt solution and basic metal or alkaline earth salt; Regulate pH between 11～13; Inject the continuous extraction case; Adding extraction agent T-BAMBP extracts; Said extraction agent add-on: concentration is the extraction agent of 1mol/L and be 4: 3 by the ratio of collection solution weight, extracts the solution that leach liquor upper strata after the extraction contains cesium ion and gets into the back extraction container, extracts the solution that leach liquor lower floor after the extraction contains rubidium ion and gets into the second continuous extraction case;
Step 2, the solution that contains cesium ion that gets in the back extraction container is carried out back extraction; Adding acid solution and high purity water gets: callable extraction liquid and the cesiated salt solution that contains respective acids, and said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate, the purity of said acid solution is >=99%; Add-on is 140g～160g/L; Said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight, and said cesiated salt solution is again through the preparation of centrifugal, dry completion cesium salt; The centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns extraction process and recycles;
Step 3, the solution that contains rubidium ion that gets into the second continuous extraction case is added extraction agent T-BAMBP extract; Said extraction agent add-on: concentration be 1mol/L extraction agent with by the collection solution weight ratio be 4: 3; The leach liquor upper solution of extracting after extracting gets into the second back extraction container, and the leach liquor lower floor liquid that extracts after extracting returns in the container of step 1;
Step 4, the leach liquor upper solution that gets in the second back extraction container is carried out back extraction; Adding acid solution and high purity water gets: callable extraction liquid and the ribidium salt solution that contains respective acids, and said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate, the purity of said acid solution is >=99%; Add-on is 140g～160g/L; Said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight, and said ribidium salt solution is again through the preparation of centrifugal, dry completion rubidium salt; The centrifugal feed liquid that goes out is returned in the container of step 1, and callable extraction liquid returns extraction process and recycles.
6. working method of producing rubidium salt is characterized in that step is following:
Collect the solution after the leaching of solution that leach liquor lower floor behind the caesium solution extraction contains rubidium ion or the commercial ore that contains rubidium in step 1, the container or contain more than one the mixing solutions of lean solution or aforementioned solution of rubidium element; Regulating pH sends in the continuous extraction case after between 11～13; Adding extraction agent T-BAMBP extracts; Said extraction agent add-on: concentration be 1mol/L extraction agent with by the collection solution weight ratio be 4: 3; The solution that leach liquor upper strata after the extraction extraction contains rubidium ion gets into the back extraction container, and the leach liquor lower floor liquid that extracts after extracting returns in the container;
Step 2, the solution that contains rubidium ion that gets in the back extraction container is carried out back extraction; Adding acid solution and high purity water gets: callable extraction liquid and the ribidium salt solution that contains respective acids, and said acid solution can be carbonic acid or sulfuric acid or nitric acid or formic acid or acetate, the purity of said acid solution is >=99%; Add-on is 140g～160g/L; Said high purity water is for adding the above high purity water of 15 Ω, and add-on is 1/6～1/8 of a stripping workshop weight, and said ribidium salt solution is again through the preparation of centrifugal, dry completion rubidium salt; Callable extraction liquid returns the step 1 extraction process and recycles, and the centrifugal feed liquid that goes out is returned in the container of step 1.
7. produce the method for extracting sodium salt in caesium, the rubidium salt process for one kind, it is characterized in that step is following:
Step 1, in container, adopt lixiviation process that the ore that contains caesium, rubidium is carried out pre-treatment, leach at gained and add alkali lye in the stoste and regulate pH value to 11～13, the process leaching contains the crystallization of sodium salt;
Step 2, the crystallization that contains sodium salt is washed, behind the cooling recrystallize high-purity moisture sodium salt.
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| CN107140662A (en) * | 2017-05-05 | 2017-09-08 | 江西东鹏新材料有限责任公司 | A kind of new method for producing cesium hydroxide |
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| CN103667727B (en) * | 2012-09-07 | 2015-09-30 | 江西东鹏新材料有限责任公司 | From putting forward the method reclaiming rubidium and caesium lithium waste residue |
| CN103233124A (en) * | 2013-04-03 | 2013-08-07 | 江西东鹏新材料有限责任公司 | Method for recovering rubidium nitrate from cesium extraction waste acid |
| CN103787375A (en) * | 2014-02-19 | 2014-05-14 | 中国科学院青海盐湖研究所 | Method for extracting rubidium salt and cesium salt |
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| CN107140662A (en) * | 2017-05-05 | 2017-09-08 | 江西东鹏新材料有限责任公司 | A kind of new method for producing cesium hydroxide |
| CN107254589A (en) * | 2017-07-06 | 2017-10-17 | 河北工程大学 | A kind of rubidium caesium in t BAMBP extractions separation and Extraction salt lake bittern |
| CN108060301A (en) * | 2017-12-05 | 2018-05-22 | 北京科技大学 | A kind of method that rubidium and by-product active calcium silicate are extracted in the ore from rubidium |
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