CN103482641A - Method for separating boron from boron-containing bittern - Google Patents
Method for separating boron from boron-containing bittern Download PDFInfo
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Abstract
A method for separating boron from boron-containing bittern comprises the steps as follows: the pH value of the boron-containing bittern is adjusted to be in a range from 1 to 4; an extraction agent and a diluent are mixed, so that an extraction organic phase is obtained; the pH-value-adjusted boron-containing bittern is extracted through the extraction organic phase, so that a boron-containing organic phase is obtained; a stripping agent is used for stripping the boron-containing organic phase, so that an organic phase and a water phase are obtained; and the water phase is subjected to evaporation, concentration and crystallization, so that boric acid or borate is obtained. According to the method, monohydric alcohol, dihydric alcohol or mixed alcohol containing the monohydric alcohol and the dihydric alcohol is taken as the extraction agent, an ether insoluble in water is taken as the diluent, and the extraction agent and the diluent are mixed, so that the extraction organic phase is obtained; the pH-value-adjusted boron-containing bittern is subjected to multistage extraction through the extraction organic phase, so that the boron-containing organic phase is obtained; and the stripping agent is used for stripping the boron-containing organic phase; and the water phase is subjected to evaporation, concentration and crystallization, so that the boric acid or the borate is obtained, the boron in the boron-containing bittern is separated, and the boron separation efficiency is high.
Description
[technical field]
The present invention relates to a kind of method of separating boron in boracic brine, relate in particular to a kind of from boracic brine the method for separating boron.
[background technology]
Boric acid is a kind of important basic chemical industry raw material, and in the development of the national economy, purposes is very extensive.At present, domestic boric acid year approximately 320,000 tons of consumptions, still, output only can maintain 90,000 tons of left and right, the boron resource scarcity has threatened the relevant industries development.And containing a large amount of boron in salt lake, mainly with the form existence in liquid ore deposit, how from boracic brine, isolating highly purified boron is current problem demanding prompt solution.
At present, in boracic brine, the method for separating boron mainly contains: acidifying remove method, the precipitator method, absorption method,
The methods such as solvent extration.Because solvent extration has, selectivity is good, impurity separates thoroughly, boron rate of recovery advantages of higher, and salt lake brine is afterwards carried in boron and will be had broad application prospects.
Disclose in patent CN101676206A and CN102295296A and a kind ofly take salt lake to carry bittern after lithium be raw material, with 2-ethyl-1, the 3-hexylene glycol extracts the method for boron with the alcohol mixture of isooctyl alcohol, primary isoamyl alcohol combination respectively from bittern, the method from extraction agent volume fraction, acidity, compare, the aspect such as extraction time, extraction temperature, saturated loading capacity, concentration of anti-stripping agent, back extraction time tested, obtained the optimum process condition of alcohol mixture boron extraction from bittern, but organic the mixing of the method damaged seriously.
Process method for extracting low-concentration boracic acid in magnesium-containing brine is disclosed in patent CN101544378A.At room temperature, the bittern of the organic phase mixed with monohydroxy-alcohol and non-polar organic solvent after as complexing extractant extraction acidifying, be extracted phase, water carries out back extraction to extraction phase again, boric acid is stripped in water, the organic phase regeneration, can drop to 20-26mg/L by boron content in bittern, but can't reach in electrolytic preparation MAGNESIUM METAL process the requirement (boron content is not higher than 1mg/L) to boron content.
Patent CN102757062A discloses a kind of method containing boron extraction in the old halogen in magnesium salts lake, and it uses B in raw material
2o
3for 1000mg/L～20000mg/L, magnesium ion content is 20000mg/L～400000mg/L, focus on the selection of extraction agent, after multi-stage counter current extraction, in old halogen, boron content drops to 30mg/L, the boric acid rate of recovery reaches 95%, but still can't reach in electrolytic preparation MAGNESIUM METAL process the requirement to boron content, and the extraction agent fatty alcohol has necessarily water-solublely in old halogen, affects the bittern subsequent disposal.
[summary of the invention]
The technical problem to be solved in the present invention is to overcome prior art and separates low, organic the mixing of separation efficiency of boron in boracic brine and damage defect high, complex process, provide high, organic the mixing of a kind of separating boron efficiency to damage the simply method of separating boron from boracic brine of low, technique, the method is reduced to boron content in the aqueous solution under 1mg/L, meets in electrolytic preparation MAGNESIUM METAL process the requirement to boron content.
For solving the problems of the technologies described above, the present invention adopts following technical proposals:
A kind of from boracic brine the method for separating boron, comprise the steps:
Step S1: the pH value of regulating described boracic brine is adjusted between 1～4;
Step S2: extraction agent and mixing diluents are extracted to organic phase, and wherein, described extraction agent is monohydroxy-alcohol, dibasic alcohol or the alcohol mixture that is comprised of monohydroxy-alcohol and dibasic alcohol, and described thinner is water-fast ethers;
Step S3: by the boracic brine of described extracted organic phase extraction after the pH value is regulated, obtain the boracic organic phase;
Step S4: by the described boracic organic phase of reverse-extraction agent back extraction, obtain organic phase and water, wherein, described reverse-extraction agent is deionized water or alkaline aqueous solution; And
Step S5: described water is obtained to boric acid or borate after evaporation, concentrated, crystallization.
In the present embodiment, in step S1, described boracic brine is mother liquid of boric acid, put forward at least one in old halogen after potassium, the former bittern in salt lake, sal epsom mother liquor or magnesium nitrate mother liquor.
In the present embodiment, in step S1, in step S1, the pH value of regulating described boracic brine is adjusted between 1～4 to be specially with hydrochloric acid regulates the pH value stabilization of described boracic brine between 1～4.
In the present embodiment, in step S1, in step S2, described extraction agent and thinner by volume per-cent between 1:4～4:1.
In the present embodiment, in step S2, in step S2, described monohydroxy-alcohol is at least one in 2-second hexanol, 3-methyl butanol, described dibasic alcohol is 2-ethyl-1, the 3-hexylene glycol, 2-butyl-2-ethyl-1, the 3-hexylene glycol, 3-methyl-2, the 4-heptanediol, 2, 2, 4-trimethylammonium-1, the 3-pentanediol, 2-butyl-2-ethyl-1, ammediol, 2-methyl-2-nonyl-1, ammediol, 2, 2-diaryl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2, 2, 4-trimethylammonium-1, the 3-pentanediol, 2-methyl-3-benzyl-1, the 3-butyleneglycol, 2.2-dimethyl-1-benzyl-1, ammediol, 2, 2, 5-trimethylammonium-1, the 3-hexylene glycol, 2, 3, 5-trimethylammonium-1, the 3-hexylene glycol, 2, 3, 6-trimethylammonium-1, the 3-heptanediol, 2, 2, 6-trimethylammonium-1, at least one in the 3-heptanediol.
In the present embodiment, in step S2, described ethers is methyl-phenoxide, sherwood oil, benzene diethyl ether, dimethylbenzene, ether.
In the present embodiment, in step S3, described extraction is Centrifugical extraction, and centrifuge speed is 1500～12000r/min, and the condition of described extraction is: the complexing time is 1～20min, and extraction temperature is 10～60 ℃; During extraction, described boracic organic phase and water volume ratio are 0.2～5, and described boracic brine flow rates is 20～2000L/h.
In the present embodiment, in step S4, the condition of described back extraction is: the back extraction time is 1～20min, and the back extraction temperature is 10～30 ℃, centrifuge speed scope 1500～12000r/min; During back extraction, described organic phase and water volume ratio are 0.3～3, and described reverse-extraction agent flow rates is 80～1000L/h.
In the present embodiment, in step S4, described alkaline aqueous solution is sodium hydroxide or the potassium hydroxide aqueous solution that pH is 8～14.
Adopt technique scheme, beneficial effect of the present invention is:
The method of separating boron from boracic brine that the above embodiment of the present invention provides, with monohydroxy-alcohol, dibasic alcohol or the alcohol mixture that is comprised of monohydroxy-alcohol and dibasic alcohol are as extraction agent, take water-fast ethers as thinner, extraction agent and thinner are mixed to get to extracted organic phase by certain concentration of volume percent, and by the extracted organic phase multi-stage solvent extraction boracic brine after the pH value is regulated, thereby obtain the boracic organic phase, use again reverse-extraction agent back extraction boracic organic phase, by the water that obtains through evaporation, concentrated, obtain boric acid or borate after crystallization, realized the separation of boron in the boracic brine, separating boron efficiency is high.
In addition, the above embodiment of the present invention also provides the alcohol mixture of usining monohydroxy-alcohol, dibasic alcohol or being comprised of monohydroxy-alcohol and dibasic alcohol as extraction agent, adopt the multi-stage solvent extraction system, boron impurities in boracic brine can be reduced to below 1mg/L, can meet in electrolytic preparation MAGNESIUM METAL process the requirement to boron content.
In addition, the method for separating boron from boracic brine that the above embodiment of the present invention provides, adopt Centrifugical extraction, and the extracting power of extraction system changes little, and extraction agent holds loss rate lower than 0.2%, the extraction agent reusable edible, and cost is low, applicable to suitability for industrialized production.
[accompanying drawing explanation]
The flow chart of steps of the method for separating boron from boracic brine that Fig. 1 provides for the embodiment of the present invention.
[embodiment]
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and the specific embodiments, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Refer to Fig. 1, steps flow chart Figure 100 of the method for separating boron from boracic brine that Fig. 1 provides for the embodiment of the present invention, as can be seen from Fig. 1, from boracic brine, the method for separating boron comprises the steps:
Step S1: the pH value of regulating described boracic brine is adjusted between 1～4;
In the present embodiment, boracic brine is mother liquid of boric acid, puies forward at least one in old halogen after potassium, the former bittern in salt lake, sal epsom mother liquor or magnesium nitrate mother liquor.In above-mentioned boracic brine, the boron ionic concn is between 100mg/L-600mg/L, and magnesium ion concentration is higher, and concentration range is between 30000-234000mg/L.
Particularly, regulate the pH value stabilization of boracic brine between 1～4 with hydrochloric acid.Hydrochloric acid is preferably 30% concentrated hydrochloric acid or dilute hydrochloric acid.
Step S2: extraction agent and mixing diluents are extracted to organic phase, and wherein, extraction agent is monohydroxy-alcohol, dibasic alcohol or the alcohol mixture that is comprised of monohydroxy-alcohol and dibasic alcohol, and thinner is water-fast ethers;
In the present embodiment, extraction agent and thinner by volume per-cent between 1:4～4:1.
In the present embodiment, monohydroxy-alcohol is at least one in 2-second hexanol, 3-methyl butanol, dibasic alcohol is 2-ethyl-1, the 3-hexylene glycol, 2-butyl-2-ethyl-1, the 3-hexylene glycol, 3-methyl-2, the 4-heptanediol, 2, 2, 4-trimethylammonium-1, the 3-pentanediol, 2-butyl-2-ethyl-1, ammediol, 2-methyl-2-nonyl-1, ammediol, 2, 2-diaryl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2, 2, 4-trimethylammonium-1, the 3-pentanediol, 2-methyl-3-benzyl-1, the 3-butyleneglycol, 2.2-dimethyl-1-benzyl-1, ammediol, 2, 2, 5-trimethylammonium-1, the 3-hexylene glycol, 2, 3, 5-trimethylammonium-1, the 3-hexylene glycol, 2, 3, 6-trimethylammonium-1, the 3-heptanediol, 2, 2, 6-trimethylammonium-1, at least one in the 3-heptanediol.
In the present embodiment, ethers is preferably methyl-phenoxide, sherwood oil, benzene diethyl ether, dimethylbenzene, ether.
Be appreciated that, choose the particularly important of suitable extraction agent and thinner, technical scheme provided by the invention using monohydroxy-alcohol, dibasic alcohol or the alcohol mixture that formed by monohydroxy-alcohol and dibasic alcohol as extraction agent, take water-fast ethers as thinner, the two is mixed to get to extracted organic phase according to a certain percentage, use again reverse-extraction agent back extraction boracic organic phase, the water that obtains is obtained to boric acid or borate after evaporation, concentrated, crystallization, realized the separation of boron in the boracic brine, separating boron efficiency is high.
Step S3: by the boracic brine of extracted organic phase extraction after the pH value is regulated, obtain the boracic organic phase;
In the present embodiment, extraction is preferably Centrifugical extraction, and centrifuge speed is 1500～12000r/min.
Be appreciated that the employing Centrifugical extraction, the extracting power of extraction system changes very little, and percentage extraction still can keep more than 99% of original extraction efficiency, and extraction agent holds loss rate lower than 0.2%, the extraction agent reusable edible, and cost is low, is applicable to suitability for industrialized production.
In the present embodiment, the condition of extraction is: the complexing time is 1～20min, and extraction temperature is 10～60 ℃; During extraction, boracic organic phase and water volume ratio are 0.2～5, and the boracic brine flow rates is 20～2000L/h.
In the present embodiment, extract as multi-stage solvent extraction.Particularly, using single alcohol during as extraction agent, adopt three grades or level Four extraction system; Using alcohol mixture during as extraction agent, adopt 1～2 grade of extraction system; Or using single alcohol and alcohol mixture during as extraction agent, the mode that adopts 1-2 level single alcohol extraction system to combine with 1 grade of alcohol mixture extraction system, boron impurities in the low boron bittern of high magnesium can both be reduced to below 1mg/L, to meet in electrolytic preparation MAGNESIUM METAL process the requirement to boron content.
Be appreciated that in extraction process, do not dissolve each other due to water and organic phase, carry out centrifugal mixer, cause very large phase interface, two-phase is fully contacted, boron spreads in extraction agent through phase interface in water, through 1-20min, reaches and balances each other; According to the two-phase density difference, can produce layering by centrifugation, reach the purpose of separation with this.
Step S4: by reverse-extraction agent back extraction boracic organic phase, obtain organic phase and water, wherein, reverse-extraction agent is deionized water or alkaline aqueous solution;
In the present embodiment, the condition of back extraction is: the back extraction time is 1～20min, and the back extraction temperature is 10～30 ℃, centrifuge speed scope 1500～12000r/min; During back extraction, organic phase and water volume ratio are 0.3～3, and the reverse-extraction agent flow rates is 80～1000L/h.
In the present embodiment, alkaline aqueous solution is sodium hydroxide or the potassium hydroxide aqueous solution that pH is 8～14.
Be appreciated that by reverse-extraction agent back extraction boracic organic phase and realized separating of boron and organic phase, obtain organic phase and can realize recycling of extracted organic phase again for extracting the boron of boracic brine, reduced cost.
Step S5: water is obtained to boric acid or borate after evaporation, concentrated, crystallization.
Be appreciated that, the water of boracic obtains high-purity boric acid or borate after evaporation, concentrated, crystallization, realizes that the degree of depth removes boron, and boron content has between original 100mg/L～600mg/L, drop in 1mg/L, can meet the requirement that the magnesium solution concentration and evaporation is produced a set of magnesium products; The degree of depth is except the aqueous salt brine after boron through concentrated, crystallization, and drying obtains high purity magnesium product (as magnesium chloride or sal epsom), and can be used as the electrolytic metal magnesium raw material.
The method of separating boron from boracic brine that the above embodiment of the present invention provides, with monohydroxy-alcohol, dibasic alcohol or the alcohol mixture that is comprised of monohydroxy-alcohol and dibasic alcohol are as extraction agent, take water-fast ethers as thinner, extraction agent and thinner are mixed to get to extracted organic phase by certain concentration of volume percent, and by the extracted organic phase multi-stage solvent extraction boracic brine after the pH value is regulated, thereby obtain the boracic organic phase, use again reverse-extraction agent back extraction boracic organic phase, by the water that obtains through evaporation, concentrated, obtain boric acid or borate after crystallization, realized the separation of boron in the boracic brine, separating boron efficiency is high.
In addition, the above embodiment of the present invention also provides the alcohol mixture of usining monohydroxy-alcohol, dibasic alcohol or being comprised of monohydroxy-alcohol and dibasic alcohol as extraction agent, adopt the multi-stage solvent extraction system, boron impurities in boracic brine can be reduced to below 1mg/L, can meet in electrolytic preparation MAGNESIUM METAL process the requirement to boron content.
In addition, the method for separating boron from boracic brine that the above embodiment of the present invention provides, adopt Centrifugical extraction, and the extracting power of extraction system changes little, and extraction agent holds loss rate lower than 0.2%, the extraction agent reusable edible, and cost is low, applicable to suitability for industrialized production.
Further set forth by the following examples the present invention, these embodiment are only presented for purposes of illustration, do not limit the scope of the invention.Except dated actual conditions, the test method in embodiment is all carried out according to normal condition.
embodiment 1
Adopt method provided by the present invention separating boron from boracic brine, wherein, boracic brine is the former bittern in salt lake, and its ionic group becomes:
| Element | Mg 2+ | Cl - | Na + | K + | B | SO 4 2- |
| Content (mg/L) | 119000 | 345000 | 1500 | 4750 | 275 | 1450 |
Experimentation:
Concentrated hydrochloric acid with 30% is regulated salt lake former bittern pH to 2.0; Adopt 2.2-dimethyl-1-benzyl-1,3-PD, 2,2,5-trimethylammonium-1, the 3-hexylene glycol mixes and forms extraction agent according to the 1:1 ratio, adopts methyl-phenoxide as thinner, by above-mentioned extraction agent and thinner by volume 1:1 be mixed to get extracted organic phase; Extracted organic phase is adopted to the boracic brine of three stage countercurrent extractions after the pH value is regulated, obtain the boracic organic phase, wherein, extraction is Centrifugical extraction, centrifuge speed is 1500r/min, and the complexing time is 1min, and extraction temperature is 25 ℃, boracic organic phase and water volume ratio are 1, and the boracic brine flow rates is 20L/h; Using the aqueous sodium hydroxide solution of pH=10 as reverse-extraction agent four-stage counter-current back extraction boracic organic phase, obtain organic phase and water, wherein, the back extraction time is 1min, the back extraction temperature is 30 ℃, and centrifuge speed scope 1500r/min, during back extraction, organic phase and water volume ratio are 0.5, and the reverse-extraction agent flow rates is 80L/h; Water is obtained to boric acid or borate after evaporation, concentrated, crystallization.After above-mentioned processing, bittern middle boron content mutually is 0.95mg/L, boron removal efficiency 99.6%.
By organic phase recycle after back extraction, after continuous circulation is used 10 times, extraction efficiency 98.7%, still kept 99.1% of first extraction efficiency, and this extraction system cycling extraction-reextraction effect stability, be suitable for suitability for industrialized production.
embodiment 2
Adopt method provided by the present invention separating boron from boracic brine, wherein, boracic brine is the sal epsom mother liquor, and its ionic group becomes:
| Element | Mg2+ | Na+ | K+ | B | Cl- | SO42- |
| Content (mg/L) | 56700 | 400 | 200 | 236 | 620 | 253200 |
Experimentation:
Concentrated hydrochloric acid with 30% is regulated salt lake former bittern pH to 1.0; Adopt 2-butyl-2-ethyl-1,3-hexylene glycol, 2.2-dimethyl-1-benzyl-1,3-PD mix and form extraction agent according to the 1:1 ratio, adopt sherwood oil as thinner, by above-mentioned extraction agent and thinner by volume 1:1 be mixed to get extracted organic phase; Extracted organic phase is adopted to the boracic brine of secondary counter-current extraction after the pH value is regulated, obtain the boracic organic phase, wherein, extraction is Centrifugical extraction, centrifuge speed is 10000r/min, and the complexing time is 10min, and extraction temperature is 35 ℃, boracic organic phase and water volume ratio are 0.2, and the boracic brine flow rates is 1000L/h; Using the aqueous sodium hydroxide solution of pH=12 as reverse-extraction agent three stage countercurrent back extraction boracic organic phases, obtain organic phase and water, wherein, the back extraction time is 10min, the back extraction temperature is 20 ℃, and centrifuge speed scope 6000r/min, during back extraction, organic phase and water volume ratio are 2, and the reverse-extraction agent flow rates is 200L/h; Water is obtained to boric acid or borate after evaporation, concentrated, crystallization.After above-mentioned processing, in sal epsom mother liquor water, boron content is 0.39mg/L, boron removal efficiency 99.8%.
By organic phase recycle after back extraction, after continuous circulation is used 10 times, extraction efficiency 97.3%, still kept 97.5% of first extraction efficiency, and this extraction system cycling extraction-reextraction effect stability, be suitable for suitability for industrialized production.
embodiment 3
Adopt method provided by the present invention separating boron from boracic brine, wherein, boracic brine is the magnesium nitrate mother liquor, and its ionic group becomes:
| Element | Cl - | SO 4 2- | Ca 2+ | Mg 2+ | K + | Na + | B |
| Content (mg/L) | 7210 | 460 | 33680 | 48970 | 1270 | 5260 | 178 |
Experimentation:
Concentrated hydrochloric acid with 30% is regulated salt lake former bittern pH to 1.0; Adopt 2-second hexanol, 2-ethyl-2-butyl-1,3-PD, 2,2,4-trimethylammonium-1, the 3-pentanediol mix to form extraction agent according to the 1:1:1 ratio, adopts the benzene diethyl ether as thinner, by above-mentioned extraction agent and thinner by volume 1:1 be mixed to get extracted organic phase; Extracted organic phase is adopted to the boracic brine of three stage countercurrent extractions after the pH value is regulated, obtain the boracic organic phase, wherein, extraction is Centrifugical extraction, centrifuge speed is 8000r/min, and the complexing time is 15min, and extraction temperature is 45 ℃, boracic organic phase and water volume ratio are 2, and the boracic brine flow rates is 1000L/h; Using the aqueous sodium hydroxide solution of pH=12 as reverse-extraction agent four-stage counter-current back extraction boracic organic phase, obtain organic phase and water, wherein, the back extraction time is 15min, the back extraction temperature is 20 ℃, and centrifuge speed scope 8000r/min, during back extraction, organic phase and water volume ratio are 0.3, and the reverse-extraction agent flow rates is 600L/h; Water is obtained to boric acid or borate after evaporation, concentrated, crystallization.After above-mentioned processing, in magnesium nitrate mother liquor water, boron content is 0.65mg/L, boron removal efficiency 99.7%.
By organic phase recycle after back extraction, after continuous circulation is used 10 times, extraction efficiency 98.9%, still kept 99.2% of first extraction efficiency, and this extraction system cycling extraction-reextraction effect stability, be suitable for suitability for industrialized production.
embodiment 4
Adopt method provided by the present invention separating boron from boracic brine, wherein, boracic brine is for carrying old halogen after potassium, and its ionic group becomes:
| Element (mg/l) | Cl - | HCO 3- | SO 4 2- | Ca 2+ | Mg 2+ | K + | B | Li + |
| Numerical value | 339807 | 1992 | 9911 | 146 | 118506 | 816 | 176 | 326 |
Experimentation:
Concentrated hydrochloric acid with 30% is regulated salt lake former bittern pH to 1.0; Adopt 2-second hexanol, 2-methyl-3-benzyl-1,3-butyleneglycol, 2.2-dimethyl-1-benzyl-1, ammediol, 2,2,5-trimethylammonium-1, the 3-hexylene glycol mix to form extraction agent according to the 1:1:1:1 ratio, adopts dimethylbenzene as thinner, by above-mentioned extraction agent and thinner by volume 1:1 be mixed to get extracted organic phase; Extracted organic phase is adopted to the boracic brine of three stage countercurrent extractions after the pH value is regulated, obtain the boracic organic phase, wherein, extraction is Centrifugical extraction, centrifuge speed is 10000r/min, and the complexing time is 20min, and extraction temperature is 25 ℃, boracic organic phase and water volume ratio are 4, and the boracic brine flow rates is 1500L/h; Using the aqueous sodium hydroxide solution of pH=11 as reverse-extraction agent four-stage counter-current back extraction boracic organic phase, obtain organic phase and water, wherein, the back extraction time is 15min, the back extraction temperature is 30 ℃, and centrifuge speed scope 10000r/min, during back extraction, organic phase and water volume ratio are 1, and the reverse-extraction agent flow rates is 800L/h; Water is obtained to boric acid or borate after evaporation, concentrated, crystallization.After above-mentioned processing, carry after potassium old bittern mutually in boron content be 0.91mg/L, boron removal efficiency 99.7%.
By organic phase recycle after back extraction, after continuous circulation is used 10 times, extraction efficiency 98.5%, still kept 98.8% of first extraction efficiency, and this extraction system cycling extraction-reextraction effect stability, be suitable for suitability for industrialized production.
embodiment 5
Adopt method provided by the present invention separating boron from boracic brine, wherein, boracic brine is mother liquid of boric acid, and its ionic group becomes:
| Element (mg/l) | Cl - | HCO 3- | SO 4 2- | Ca 2+ | Mg 2+ | K + | B | Li + |
| Numerical value | 339807 | 1992 | 9911 | 146 | 118506 | 816 | 176 | 326 |
Experimentation:
Regulate salt lake former bittern pH to 3.0 with dilute hydrochloric acid; Adopt 2-second hexanol, 3-methyl butanol, 2-ethyl-1,3-hexylene glycol, 2-butyl-2-ethyl-1, the 3-hexylene glycol mix to form extraction agent according to the 1:1:1:1 ratio, adopts ether as thinner, by above-mentioned extraction agent and thinner by volume 1:1 be mixed to get extracted organic phase; Extracted organic phase is adopted to the boracic brine of secondary counter-current extraction after the pH value is regulated, obtain the boracic organic phase, wherein, extraction is Centrifugical extraction, centrifuge speed is 12000r/min, and the complexing time is 20min, and extraction temperature is 25 ℃, boracic organic phase and water volume ratio are 5, and the boracic brine flow rates is 2000L/h; Using the potassium hydroxide aqueous solution of pH=13 as reverse-extraction agent three stage countercurrent back extraction boracic organic phases, obtain organic phase and water, wherein, the back extraction time is 20min, the back extraction temperature is 30 ℃, and centrifuge speed scope 10000r/min, during back extraction, organic phase and water volume ratio are 3, and the reverse-extraction agent flow rates is 1000L/h; Water is obtained to boric acid or borate after evaporation, concentrated, crystallization.After above-mentioned processing, in the mother liquid of boric acid water, boron content is 0.85mg/L, boron removal efficiency 99.6%.
By organic phase recycle after back extraction, after continuous circulation is used 10 times, extraction efficiency 99.0%, still kept 99.4% of first extraction efficiency, and this extraction system cycling extraction-reextraction effect stability, be suitable for suitability for industrialized production.
embodiment 6
Adopt method provided by the present invention separating boron from boracic brine, wherein, boracic brine is the sal epsom mother liquor, and its ionic group becomes:
| Element | Mg 2+ | Cl - | Na + | K + | B | SO 4 2- |
| Content (mg/L) | 122000 | 325000 | 1620 | 865 | 358 | 34000 |
Experimentation:
Regulate salt lake former bittern pH to 4.0 with dilute hydrochloric acid; Adopt primary isoamyl alcohol, 2-butyl-2-ethyl-1,3-hexylene glycol, 2-ethyl-2-butyl-1, ammediol mix to form extraction agent according to the 1:1:1 ratio, adopts methyl-phenoxide as thinner, by above-mentioned extraction agent and thinner by volume 1:1 be mixed to get extracted organic phase; Extracted organic phase is adopted to the boracic brine of secondary counter-current extraction after the pH value is regulated, obtain the boracic organic phase, wherein, extraction is Centrifugical extraction, centrifuge speed is 12000r/min, and the complexing time is 20min, and extraction temperature is 25 ℃, boracic organic phase and water volume ratio are 0.5, and the boracic brine flow rates is 2000L/h; Using the potassium hydroxide aqueous solution of pH=11 as reverse-extraction agent three stage countercurrent back extraction boracic organic phases, obtain organic phase and water, wherein, the back extraction time is 20min, the back extraction temperature is 30 ℃, and centrifuge speed scope 10000r/min, during back extraction, organic phase and water volume ratio are 1, and the reverse-extraction agent flow rates is 1000L/h; Water is obtained to boric acid or borate after evaporation, concentrated, crystallization.After above-mentioned processing, in sal epsom mother liquor water, boron content is 0.98mg/L, boron removal efficiency 99.7%.
By organic phase recycle after back extraction, after continuous circulation is used 10 times, extraction efficiency 98.9%, still kept 99.1% of first extraction efficiency, and this extraction system cycling extraction-reextraction effect stability, be suitable for suitability for industrialized production.
The above, it is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, although the present invention discloses as above with preferred embodiment, yet not in order to limit the present invention, any those skilled in the art, within not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be not break away from the technical solution of the present invention content, any simple modification of above embodiment being done according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (9)
1. the method for a separating boron from boracic brine, is characterized in that, comprises the steps:
Step S1: the pH value of regulating described boracic brine is adjusted between 1～4;
Step S2: extraction agent and mixing diluents are extracted to organic phase, and wherein, described extraction agent is monohydroxy-alcohol, dibasic alcohol or the alcohol mixture that is comprised of monohydroxy-alcohol and dibasic alcohol, and described thinner is water-fast ethers;
Step S3: by the boracic brine of described extracted organic phase extraction after the pH value is regulated, obtain the boracic organic phase;
Step S4: by the described boracic organic phase of reverse-extraction agent back extraction, obtain organic phase and water, wherein, described reverse-extraction agent is deionized water or alkaline aqueous solution; And
Step S5: described water is obtained to boric acid or borate after evaporation, concentrated, crystallization.
According to claim 1 from boracic brine the method for separating boron, it is characterized in that, in step S1, described boracic brine is mother liquid of boric acid, put forward at least one in old halogen after potassium, the former bittern in salt lake, sal epsom mother liquor or magnesium nitrate mother liquor.
According to claim 1 from boracic brine the method for separating boron, it is characterized in that, in step S1, the pH value of regulating described boracic brine is adjusted between 1～4 to be specially with hydrochloric acid regulates the pH value stabilization of described boracic brine between 1～4.
According to claim 1 from boracic brine the method for separating boron, it is characterized in that, in step S2, described extraction agent and thinner by volume per-cent between 1:4～4:1.
According to claim 1 from boracic brine the method for separating boron, it is characterized in that, in step S2, described monohydroxy-alcohol is at least one in 2-second hexanol, 3-methyl butanol, described dibasic alcohol is 2-ethyl-1, the 3-hexylene glycol, 2-butyl-2-ethyl-1, the 3-hexylene glycol, 3-methyl-2, the 4-heptanediol, 2, 2, 4-trimethylammonium-1, the 3-pentanediol, 2-butyl-2-ethyl-1, ammediol, 2-methyl-2-nonyl-1, ammediol, 2, 2-diaryl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2, 2, 4-trimethylammonium-1, the 3-pentanediol, 2-methyl-3-benzyl-1, the 3-butyleneglycol, 2.2-dimethyl-1-benzyl-1, ammediol, 2, 2, 5-trimethylammonium-1, the 3-hexylene glycol, 2, 3, 5-trimethylammonium-1, the 3-hexylene glycol, 2, 3, 6-trimethylammonium-1, the 3-heptanediol, 2, 2, 6-trimethylammonium-1, at least one in the 3-heptanediol.
According to claim 1 from boracic brine the method for separating boron, it is characterized in that, in step S2, described ethers is methyl-phenoxide, sherwood oil, benzene diethyl ether, dimethylbenzene, ether.
According to claim 1 from boracic brine the method for separating boron, it is characterized in that, in step S3, described extraction is Centrifugical extraction, centrifuge speed is 1500～12000r/min; The condition of described extraction is: the complexing time is 1～20min, and extraction temperature is 10～60 ℃; During extraction, described boracic organic phase and water volume ratio are 0.2～5, and described boracic brine flow rates is 20～2000L/h.
According to claim 1 from boracic brine the method for separating boron, it is characterized in that, in step S4, the condition of described back extraction is: the back extraction time is 1～20min, the back extraction temperature is 10～30 ℃, centrifuge speed scope 1500～12000r/min; During back extraction, described organic phase and water volume ratio are 0.3～3, and described reverse-extraction agent flow rates is 80～1000L/h.
According to claim 1 from boracic brine the method for separating boron, it is characterized in that, in step S4, described alkaline aqueous solution is sodium hydroxide or the potassium hydroxide aqueous solution that pH is 8～14.
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