CN104445242B - Use the attached method carrying boron in combination of solvent extraction-ion-exchange absorption - Google Patents
Use the attached method carrying boron in combination of solvent extraction-ion-exchange absorption Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
- C01B35/1054—Orthoboric acid
- C01B35/1081—Preparation by working up other natural sources, e.g. seawater
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
- C01B35/1054—Orthoboric acid
- C01B35/109—Purification; Separation; Concentration
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Abstract
The present invention relates to a kind of use the attached method carrying boron in combination of solvent extraction ion-exchange absorption.After the heavy boron of acidifying containing the boric acid extracting lower content magnesium salts lake bittern.The extraction process using less progression can effectively reduce energy consumption, and reduces the consumption of extractant.Combine the attached operation of ion-exchange absorption after extraction, use Exchange Resin by Adsorption highly selective to remove the boron element of eliminating minute, be effectively reduced boron extraction progression, reduce energy consumption；Using new mixed extractant system, single-stage extraction rate is high, and molten damage is few.The enforcement of this invention can be under conditions of low energy consumption, the boron of low content in old halogen after effectively extraction salt lake is acidified heavy boron, extract is pure boron-containing solution, high-quality boron product can be prepared, boron resource is made to be fully used, and make the quality of follow-up magnesium salts product be greatly improved, it is achieved the comprehensive development and utilization of the old halogen after the heavy boron of salt lake acidifying, and significantly improve economic benefit.
Description
Technical field
The present invention relates to a kind of Comprehensive Utilization of Bittern Resources and comprehensive utilization novel technique, belong to chemical industry of inorganic salt technical field,
It is specifically related to a kind of use the attached method carrying boron in combination of solvent extraction-ion-exchange absorption.
Background technology
Boron and boron compound have a wide range of applications at agricultural, metallurgy, national defence, the aspect such as mechanical and medical, and along with China's work
The fast development of industry, demand grows with each passing day.At present, China's solid boron resource is closely exhausted through exploitation for many years, boron-rich
Salt lake bittern resources advantage highlights, and is the most not yet effectively utilized exploitation.Therefore, from bittern, separation and Extraction boron element will
It is to obtain boron element and the main path of boron compound from now on.
In the comprehensive development and utilization of salt lake bittern, containing potassium, magnesium, the bittern of boron, after extracting potassium, concentrate the heavy boron of acidifying,
Major part boron element separates out with the form of boric acid, remains low boracic (with B2O3Meter about 10g/L) aqueous salt brine of high magnesium chloride containing,
It is referred to as old halogen after the heavy boron of salt lake acidifying.This aqueous salt brine can be used to produce magnesium chloride, magnesium hydroxide and magnesium carbonate etc..But due to
The existence of low content boron element, drastically influence the quality of subsequent product.Use and suitable put forward boron method, after being possible not only to improve
The quality of the products such as continuous magnesium, and the boron resource in salt lake bittern can be made to obtain abundant extraction and application.
The method extracting boron element from salt lake bittern has the precipitation method, floatation, acidization, ion-exchange and solvent extraction
And additive method etc., wherein, extraction receives publicity in terms of low concentration carries boron, and ion-exchange carries in very lower loading
Boron aspect demonstrates advantage.Extractant mainly includes monohydric alcohol, dihydroxylic alcohols, mixed alcohol, hydroxylamine, hydroxyl oxime, polyvinyl alcohol etc..
Relevant domestic and international patent and paper etc. see progress report (Xu and Jiang, Ind.Eng.Chem.Res.2008,47 (1):
16-24；Xiong Yan etc., chemical industry is in progress, and 2012,31 (8): 1647-1655).Achievement in research afterwards refers to pertinent literature (Lu
Jian Hua etc., Journal of Chemical Industry and Engineering, 2012,63 (S1): 145-153；Xiong Yan etc., Journal of Chemical Industry and Engineering, 2012,63 (11): 3546-3552；
Zhao Xianyin etc., chemical industry mineral and processing, 2012, (5): 16-19；Jiang Yunjiang etc., Minerals And Rocks, 2013,33 (3): 26-29；
Zhang Xiufeng etc. (chemical industry mineral and processing, 2013, (1): 5-8)；Zhang Lizhen etc., chemical industry mineral and processing, 2013, (1):
9-12；Zhang Lizhen etc., inorganic chemicals industry, 2013,45 (4): 15-17；Xiao Meiling etc., chemical industry mineral and processing, 2013,
(11): 9-13；Xie Yunrong etc., Chemical Industry in Guangzhou, 2013,41 (11): 100-102；Lu Jianhua etc., Chin.J.Chem.
Eng., 2014,22 (5): 496-502).The main patent document of some of them is briefly described below.
Lv Jianhua etc. (Journal of Chemical Industry and Engineering, 2012,63 (S1): 145-153) have studied 2-ethyl-1,3-hexylene glycol extraction boric acid
Mass tranfer coefficient.Xiong Yan etc. (Journal of Chemical Industry and Engineering, 2012,63 (11): 3546-3552) have studied 1,3-binary aliphatic alcohol extraction boric acid
Equilibrium response.Zhao Xianyin etc. (chemical industry mineral and processing, 2012, (5): 16-19) are using isooctanol as extractant, sulfonation
Kerosene is diluent, has investigated isooctanol to the impact of boron extraction in brine of oil field.Jiang Yunjiang etc. (Minerals And Rocks, 2013,33
(3): 26-29) have studied the subsurface brine that falls to normal price with the Sichuan Basin as raw material, 2,2,4-trimethyl-1,3-pentanediol is extractant,
CHC13For diluent boron extraction from bittern, it is thus achieved that 2,2,4-trimethyl-1,3-pentanediol is from the subsurface brine that falls to normal price
Carrying the optimal condition of boron: when extractant concentration is 0.8mol/L, be in a ratio of 1:1, bittern pH=1～6, extraction time is
During 8min, saturated loading capacity is that 46.25g/L is (with H3BO3Meter), extract through one-level under this condition, two grades of back extractions, boron
The rate of recovery reach 90.62%.Zhang Xiufeng etc. (chemical industry mineral and processing, 2013, (1): 5-8) use Solvent Extraction Separation to carry
Taking the boron in Jiangling Depression deep layer potassium-rich brine, result shows, with 2-ethyl-1 that volume fraction is 15%, 3-hexylene glycol,
The mixed alcohol of 35% isooctanol is extractant, and 50% sulfonated kerosene is diluent, and it is 15min that extraction is in a ratio of 1:1. extraction time
Under conditions of, boron single-stage extraction rate reaches more than 95%.To the west of Zhang Lizhen etc. (chemical industry mineral and processing, 2013, (1): 9-12)
Hiding Lake Jiezechaka salt lake bittern is raw material, uses D564 effects of boron resin to carry out the experimental study of the attached boron of ion-exchange absorption, knot
Fruit shows, the resin adsorption rate to boron > 97%, B in liquid after suction2O3< 50mg/L, D564 are in complex system for mass concentration
Boron is had high selectivity.They (inorganic chemicals industry, 2013,45 (4): 15-17) also with Tibet salt lake bittern concentrate
For research object, the factors of impact extraction and back extraction is carried out detailed test study, it is thus achieved that mixing alcohol extracting boron is suitable
Extraction conditions: material liquid pH=3, the volume ratio (2-ethyl-1,3-hexylene glycol) of mixed alcohol extractant and sulfonated kerosene: (different pungent
Alcohol): (sulfonated kerosene)=3:7:10, it is in a ratio of 1.0, extraction time is 10min: back extraction condition: strippant concentration is 0.3
Mo1/L, is in a ratio of 1.0, and back-extraction time is 10min.Under these process conditions, extraction yield > 96%, stripping rate > 95%.
Extracting boron using the mixed alcohol of dihydroxylic alcohols Yu monohydric alcohol as extractant, effect of extracting is much better than monohydric alcohol.(the chemical industry ore deposit such as Xiao Meiling
Thing and processing, 2013, (11): 9-13) with 2-ethyl-l, 3-hexylene glycol and isooctanol are by certain volume ratio composition hybrid extraction
Agent, sulfonated kerosene are the boron in the diluent extraction old halogen of West Taijinar Salt Lake, and result shows: when 2-ethyl-1,3-hexylene glycol,
Isooctanol and sulfonated kerosene volume ratio are 2:3:5, and brine ph is 2, and organic phase and aqueous phase volume ratio are l:1, during extraction
Between when being 6min, single-stage extraction rate is 95.19%, and through 2 grades of extractions, the extraction yield of boric acid is up to 99.06%.Boron in old halogen
Overall recovery reach 97.13%.It is worth mentioning that Tural etc. (Turkish J.Chem., 2007,3l:163-170) and
Karakaplan etc. (Solvent Extraction Ion Exchange, 2004,22 (6): 897-911) have studied some dihydroxylic alcohols
Boric acid extraction ability, finds 2,2, and 4-trimethyl-1,3-pentanediol preferably carries effect of boron.(the Indian J.Chem. such as Mohapatra
Tech., 2008,15 (9): 483-487) use 2,2,4-trimethyl-1,3-pentanediol to be dissolved in carbon tetrachloride and reclaim liquid crystal as extractant
Boron element in display industrial wastewater, it is thus achieved that the boron extraction yield of 99% and the back extraction ratio of 97%.Zhang Baowen (steel research journal,
1983,3 (1): 144-148) using 2,2,4-trimethyl-1,3-pentanediol has carried out the research of Determination of Trace Boron, has investigated emphatically this reagent
In highly acidity medium, extract the condition of boron, and use it for measuring Determination of Trace Boron in steel, without boron sulfuric acid, the preparation of phosphoric acid.But,
Carbon tetrachloride has toxicity, is limited using carbon tetrachloride as its application of the extractant of solvent；Single 2,2,4-trimethyl-1,
3-pentanediol is as extractant, the boracic brine to high-load, and demonstrates excellent extraction ability, and does not have cost advantage.
CN101544378B proposes a kind of process method for extracting low-concentration boracic acid in magnesium-containing brine.With monohydric alcohol (butanol, oneself
Alcohol, enanthol or decyl alcohol) with non-polar organic solvent formed mixed solvent as complexing extractant extraction acidifying after bittern,
To extraction phase, then with water, extraction phase being carried out back extraction, borated aqueous phase carries out concentration and evaporation, obtains boric acid product, extraction
Rear bittern Boron contents can be down to 20mg/L.CN102757062B discloses a kind of from containing the method for boron extraction magnesium salts lake bittern.
This method uses 1 containing aryl, and 3-binary aliphatic alcohol, for carrying boron extractant, is made with the mixed solution that diluent forms by carrying boron extractant
For extraction organic phase, carrying out multitple extraction with material liquid, extraction progression mostly is 3～6 grades, obtains borated extraction phase.Afterwards
With aqueous alkali as back washing agent, carry out the back extraction of same progression, it is thus achieved that boron water solution.This method can be by magnesium-containing brine mesoboric acid
Content drops to below 30mg/L, obtains tincal product simultaneously.Single-stage boric acid extraction yield reaches more than 90%, and boric acid yield reaches
More than 95%, solvent consumption is the most less.But the extraction of this method and stripping steps are more, cause energy consumption high and water usage is big.
CN103508462A provides a kind of potassium, boron, the method for lithium in comprehensive utilization carbonate-type (Tibet) salt lake bittern, passes through
Introduce acidification technique and bittern type is converted into chloride type by carbonate-type, make bittern composition simplify, thus combined extracting potassium,
Boron, lithium.The method use acidification technique adjust brine ph, to acidifying after bittern use solvent (isooctanol or 2-ethyl, 1,
One or both of 3-ethylene glycol) extraction extracts boric acid；Raffinate enters sodium salt pond, and solar evaporation separates out sodium salt, enters afterwards
Sylvite pond separates out potassium mixed salt；Floatation is used to purify potassium mixed salt preparing potassium chloride；The precipitation method are used to carry in the analysis potassium mother liquor of enriching lithium
Take lithium carbonate, carry the old halogen after lithium and be back to acidification pool and recycle.CN103482643A has invented a kind of from boracic brine
The method of separating boron.The method is with monohydric alcohol (at least one in 2-second hexanol, 3-methyl butanol), dihydroxylic alcohols (2-ethyl-1,3-
Ethylene glycol, 2,2,4-trimethyl-1,3-pentanediol etc.) or the mixed alcohol that is made up of monohydric alcohol and dihydroxylic alcohols be extractant, with alkanes
For diluent, extractant and diluent are mixed to get extraction organic phase, and extraction organic phase multitple extraction is regulated through pH value
After boracic brine, thus obtain boracic organic phase, then by back washing agent back extraction boracic organic phase, by the aqueous phase that obtains through evaporation,
Boric acid or borate is obtained, it is achieved the separation of boron in boracic brine after concentration, crystallization.
CN101565188A has invented the technique of a kind of preparing borax from brine, including: raw brine is extracted with unitary mixed alcohols
Take agent 1:1 in mass ratio～3 mixing, by continuous countercurrent technique extraction feed bittern, obtain raffinate phase and extraction phase；By above-mentioned extraction
Xiang Yushui 1:0.1 in mass ratio～3 mixing, carries out back extraction by continuous countercurrent technique, obtains anti-stripping agent；Adjust above-mentioned back extraction
Liquid pH8～10, stirring cooling, form borax sediment, filter, obtain solid-state borax decahydrate.
CN103031448A reports a kind of There-liquid-phase extraction preenrichment and the method separating Lithium from Salt Lake Brine and boron, bag
Include: in the concentrated brine solution of salt lake, add water-soluble synergic reagent, regulate bittern pH, be subsequently adding high molecular weight water soluble polymer
(polymer diol class), is sufficiently mixed under room temperature and obtains upper and lower two-layer liquid-phase system；Be subsequently adding organic extractant (organic phosphates,
A lot), upper, middle and lower-ranking liquid-phase system is obtained after mixing.Taking the two-phase upper, middle of three liquid-phase systems, back extraction reclaims it respectively
In lithium and boron.
CN 103896296A discloses a kind of air supporting polymer method and apparatus from salt lake bittern boron extraction, and the method utilizes
Air supporting extraction column completes, and utilizes water-soluble polymer to form polymer molecule microscopic aggregates trapping boron in salt lake bittern, then
Air supporting trapping boron polymer molecule microscopic aggregates.
CN101318675A discloses a kind of method of removing boron and iron from boron containing magnesium chloride saturated liquid.This method is with boron containing magnesium chloride
Saturated solution is raw material, the technique that after using first acidifying, unitary mixed alcohol extracts, and adds hydrochloric acid or sulfuric acid acid precipitation boric acid, then
With remaining boric acid in mixed alcohol extraction removing acidifying solution.The boric acid rate of recovery reaches more than 99%.But this method is adopted at alcohol extraction process
By 5～10 grades of extractions and 5～8 grades of reverse extraction technology, energy consumption is higher, and water consumption is big, and this is one in the area of shortage of water resources
Major issue.
CN101538048A reports a kind of method that acidization-extraction method extracts boric acid from boron containing magnesium chloride solution.This method is adopted
With acidifying, filter, repeatedly extraction, repeatedly back extraction, be provided with after filtering technique thermosol decolouring, filter slag tap, crystallisation by cooling filter,
Evaporating four operations, crystallisation by cooling obtains boric acid product after filtering.Main chain is obtained with isoamyl alcohol in 1:20 ratio is compounding with sec-octyl alcohol
Containing C5～8 branched unitary mixed alcohol, unitary mixed alcohol sulfonated kerosene must compound extractant by 1:1 dilution proportion.Extractant
Carrying out boric acid remaining in acidifying solution further reclaiming the process extracted, the rate of recovery of final boron reaches more than 95%.
CN102295296A disclose a kind of with 2-ethyl-1,3-hexylene glycol respectively with isooctanol, isoamyl alcohol combination mixed alcohol from
Salt lake carry lithium after bittern in extract the technique of boron, it is thus achieved that most preferably put forward boron process conditions.
CN200810157162 discloses and a kind of carry bittern after lithium with salt lake and put forward boron method as raw material, and this invention is from extractant volume
Mark, acidity, compare, extraction time, extraction temperature, saturated loading capacity, concentration of anti-stripping agent, the aspect such as Stripping times add
With experiment, it is thus achieved that mixed alcohol (2-ethyl-1,3-hexylene glycol respectively with isooctanol, isoamyl alcohol composition mixed alcohol) from bittern
The optimum process condition of boron extraction.
Additionally, CN101691229B disclose a kind of bicarbonate desorb adsorbed by magnesium hydrate precipitate potassium, sodium, lithium,
The method of boron.Magnesium is changed into magnesium hydrate precipitate by bittern alkaline chemical precipitation by this method, during adsorbed potassium more in bittern,
The element such as sodium, lithium boron；Then by adding bicarbonate solution more than the operations such as reaction, separation of solid and liquid of sizing mixing, stir are incited somebody to action again
Element desorbs from magnesium hydroxide, the element such as recyclable 90% potassium adsorbed by magnesium hydrate precipitate, sodium, lithium, boron.In
State's patent CN100528753C has been invented a kind of with salt lake boracic, magnesium, lithium bittern as raw material, combined extracting from salt lake bittern
Boron, magnesium, the method for lithium, wherein put forward boron operation and mainly use sulfuric acid or hydrochloric acid method preparing boric acid, carried out with centrifuge or filter press
Filter isolated boric acid and boron removal bittern.
Although the most existing multiple report putting forward boron process from salt lake bittern, but still suffer from many deficiencies.Such as, acidifying
Although crystallisation equipment is simple, with short production cycle, but is primarily adapted for use in the extraction of high-load boron element, and boron element is difficult to obtain
Extraction more thoroughly separates；The elements such as potassium, sodium, lithium, boron are adsorbed by adsorption coprecipitation method simultaneously, still need to later separation；
Using solvent extraction, the most more to the extraction needed for obtaining the high boric acid rate of recovery and back extraction progression, energy consumption is high, and uses water
Amount is big；Although ion-exchange adsorptive selectivity is higher, but due to the attached appearance quantitative limitation of its ion-exchange absorption, inapplicable higher contain
The extraction of amount boracic brine.And the various extractions reported carry in boron technique, still do not have the technology can be with energy-efficient economical real
Land used carries boron for the degree of depth of salt lake bittern, needs to develop the fruitful salt lake bittern degree of depth further and carries boron new process.
Summary of the invention
For the deficiency of existing process, it is an object of the invention to provide a kind of employing attached associating of solvent extraction-ion-exchange absorption
The method carrying boron, after the heavy boron of acidifying containing the boric acid extracting lower content magnesium salts lake bittern.The enforcement of this New process combining
The boron element of low content in salt lake bittern can be extracted efficiently, makes boron resource be fully used under conditions of low energy consumption, and
The product qualities such as the magnesium making subsequent production are greatly improved, it is achieved the comprehensive development and utilization of salt lake bittern, and significantly improve through
Ji benefit.
To this end, present invention employs following technical scheme:
Use the attached method carrying boron in combination of solvent extraction-ion-exchange absorption, comprise the steps:
(1) at room temperature, by the pH value of NaOH solution regulation salt lake bittern 1～5；
(2) preparation mixed extractant system: the mixed alcohol using 2,2,4-trimethyl-1,3-pentanediol and Decanol, isooctanol is extraction
Taking medium, tributyl phosphate is conditioning agent, and aviation kerosine is solvent, forms mixed extractant system；Wherein, aviation kerosine: just
Decyl alcohol: isooctanol: tributyl phosphate volume ratio=100:(36～68): (30～60): (2～4)；2,2,4-trimethyl-1,3-penta
Glycol consumption accounts for the 1～5% of total extractant quality；Addition 2,2,4-trimethyl-1, after 3-pentanediol, formed after agitated abundant dissolving
Total extractant；
(3) by the salt lake bittern after the extraction acidifying of total extractant, total extractant system is 1:1～3:1 with the volume ratio of salt lake bittern；
Extraction progression is 1～3 grade, is extracted in organic phase by the boric acid in bittern, is extracted phase；Boron in raffinate phase is made to contain after extraction
Amount is with B2O3Meter is reduced to below 300mg/L；
(4) NaCl solution that the boron element in organic extraction mutually uses pH value to be 7～13 carries out back extraction, NaCl solution with have
The volume ratio of machine phase is 1:1～3:1, and back extraction progression is 1～3 grade；The Boron contents aqueous solution more than 0.5g/L is obtained after back extraction；
(5) Boron contents is less than to the raffinate phase of 300mg/L, uses the NaOH solution of 0.5～5mol/L its pH value to be adjusted to
4～9；
(6) raffinate phase less than 300mg/L of the Boron contents after pH value regulates, adds boron selective ion exchanger resin；Ion
Remaining boron element in exchange adsorption salt lake bittern, ion exchange resin consumption is every liter of bittern 6～40g resin；Ion-exchange absorption
Attached complete after, through filter bittern can be separated with ion exchange resin, in bittern, Boron contents can be reduced to below 5mg/L；
(7) ion exchange resin of absorption boron element uses the hydrochloric acid solution of 0.05～0.5mol/L to elute, and obtains Boron contents and is more than
The boracic aqueous phase of 35mg/L, obtains boric acid product through evaporative crystallization, or re-start after returning the mixing of crude salt lake bittern extraction-from
Sub-exchange adsorption combined separation carries boron.
Described step (1) NaOH solution concentration is 0.5～5mol/L；Preferably NaOH solution concentration is 0.5～2mol/L.Preferably
The pH 2～3 of NaOH regulation salt lake bittern.
Described step (3) extraction progression is preferably 1～2 grade.
Boron element in described step (4) organic extraction mutually uses the NaCl solution of pH value preferably 10～11 to carry out back extraction,
In NaCl solution, the concentration of NaCl is 2.5～50g/L；Organic phase returns mixed extractant and is reused for salt lake bittern extraction process.
Described step (5) pH value is preferably adjusted to 7～9.
Described step (6) ion exchange resin uses macropore polystyrene resin (ps) D564, Diaion CRB 02, Diaion CRB
One in 01；Remaining boron element in ion-exchange absorption attached salt lake bittern, ion exchange resin consumption is 6～40g (resin)/L (halogen
Water).
6～18g/L are preferably for D564 ion exchange resin consumption；For Diaion CRB02, Diaion CRB01 ion
Exchanger resin consumption is preferably 30～40g/L.
The concentration of described step (7) hydrochloric acid is 0.3～0.5mol/L；The volume of hydrochloric acid solution used and process salt lake bittern volume phase
Deng.
The prominent technological merit of the present invention:
The process carrying boron after the heavy boron of the acidifying containing magnesium salts lake that the present invention provides in old halogen uses the attached associating of extraction-ion-exchange absorption
Put forward boron new technology, use the extraction process of less progression can effectively reduce energy consumption, and reduce the consumption of extractant.Combine after extraction
The attached operation of ion-exchange absorption, uses Exchange Resin by Adsorption highly selective to remove the boron element of eliminating minute, is effectively reduced boron
Extraction progression, reduces energy consumption；Using new mixed extractant system, single-stage extraction rate is high, and molten damage is few.The enforcement of this invention can
Under conditions of low energy consumption, the boron of low content in old halogen after effectively extraction salt lake is acidified heavy boron, extract is pure boron-containing solution,
High-quality boron product can be prepared, make boron resource be fully used, and make the quality of follow-up magnesium salts product be greatly improved,
Realize the comprehensive development and utilization of the old halogen after the heavy boron of salt lake acidifying, and significantly improve economic benefit.
Accompanying drawing explanation
After the heavy boron of Fig. 1 acidifying containing magnesium salts lake, old halogen proposes boron technological process extraction-ion-exchange absorption attached associating.
Detailed description of the invention
The process step of the invention and result is described in detail below in conjunction with the accompanying drawings with specific embodiment.Containing in magnesium salts lake bittern extract-from
Sub-exchange adsorption is combined and is carried the idiographic flow of boron new technology as shown in Figure 1.
For after the salt lake bittern heavy boron of acidifying containing magnesium salts lake bittern, after using first extraction, attached the combining of ion-exchange absorption puies forward the new work of boron
The product matter such as skill, fully extracts remaining boron element from salt lake bittern, and make rich magnesium bittern be purified, the magnesium of subsequent production
Amount is also greatly enhanced.Present invention is generally directed to the salt lake bittern after being acidified heavy boron, wherein Boron contents is (with B2O3Meter) little
In 11g/L.
First, by the pH value of NaOH solution regulation salt lake bittern between 1～3, boron extraction is then carried out；Boron extraction is adopted
The volume ratio of extractant system and salt lake bittern be (1～3): 1, extracting progression is 1～3 grade, makes raffinate phase (aqueous salt brine)
Middle Boron contents is (with B2O3Meter) it is reduced to about below 300mg/L, then molten by the bittern after NaOH solution regulation boron extraction
The pH value of liquid is 4～9, adds boron selective ion exchanger resin particle, and it is surplus that mechanical agitation makes ion exchange resin fully adsorb
The borate ion of remaining low content, can make the Boron contents in salt lake bittern (with B after filtration2O3Meter) it is reduced to below 5mg/L；
The boracic extraction phase of extraction process gained, after the sodium chloride solution back extraction of distilled water or low content NaCl, evaporative crystallization obtains
To tincal product；The ion exchange resin that ion-exchange absorption is attached, after chlorohydric acid pickling, solution returns the lake bittern water raw material Han magnesium salts
In liquid, and ion exchange absorbent also can obtain regeneration.
Present invention is alternatively directed to salt lake bittern put forward boron operation and develop a kind of extractant system.This extractant system uses 2,2,4-trimethyl
The mixed alcohol of-1,3-pentanediol and Decanol, isooctanol is spe medium, and tributyl phosphate is conditioning agent, and aviation kerosine is solvent,
Form mixed extractant system.It is high that this extractant system has extraction efficiency, and the molten damage of aqueous phase is little, low cost, and flash-point is high, back extraction
It is difficult to the advantages such as foaming under pH value higher in operation.Ion exchange resin uses macropore polystyrene resin (ps) D564, Diaion
One in CRB 02, Diaion CRB 01.
What the present invention provided specifically includes following steps containing the process carrying boron in magnesium salts lake bittern:
(1) at room temperature, with 0.5～5mol/L NaOH solution regulate salt lake bittern pH value between 1～5, NaOH
Solution concentration preferably 0.5～2mol/L, the pH value of salt lake bittern regulates preferably 2～3.
(2) preparation mixed extractant system: the mixed alcohol using 2,2,4-trimethyl-1,3-pentanediol and Decanol, isooctanol is extraction
Taking medium, tributyl phosphate is conditioning agent, and aviation kerosine is solvent, forms mixed extractant system；Wherein, aviation kerosine,
Decanol, isooctanol, the volume ratio of tributyl phosphate are aviation kerosine: Decanol: isooctanol: tributyl phosphate=100:(36～68):
(30～60): (2～4).Due to 2,2,4-trimethyl-1, are solid under 3-pentanediol normal temperature, therefore 2,2,4-trimethyl-1,3-penta 2
Alcohol consumption uses mass fraction metering, and its addition accounts for the 1～5% of total extractant quality；Add 2,2,4-trimethyl-1,3-pentanediol
After, form total extractant system after agitated abundant dissolving.
(3) by the salt lake bittern after the extraction acidifying of mixed extractant system, extractant system controls with the volume ratio of salt lake bittern
1:1～3:1；Extraction progression is 1～3 grade, preferably 1～2 grade, is extracted in organic phase by the boric acid in bittern, is extracted phase；
Make in raffinate phase (aqueous salt brine) Boron contents (with B after extraction2O3Meter) it is reduced to below 300mg/L.
(4) NaCl solution that the boron element in organic extraction mutually uses pH value to be 7～13 carries out back extraction, NaCl solution with have
The volume ratio of machine phase is 1:1～3:1, and back extraction progression is 1～3 grade.Wherein, the pH value of solution preferably 10～11, use NaCl
Solution can effectively prevent the molten damage of extractant, and in NaCl solution, the concentration of NaCl is 2.5～50g/L, preferential 5～10g/L.Back extraction
After obtain the aqueous solution that Boron contents is 0.500～1.088g/L, this concentration is the volume that the titrating solution measured of titrimetry consumes,
Then converse concentration, i.e. can get tincal product through evaporative crystallization；Organic phase can return to mixed extractant, and to be reused for salt lake old
Halogen extraction process.
(5) Boron contents being less than to the raffinate phase (aqueous salt brine) of 300mg/L, the NaOH solution of employing 0.5～5mol/L is by it
PH value is adjusted to 4～9, and wherein preferable ph is 7～9.
(6) raffinate phase (aqueous salt brine) less than 300mg/L of the Boron contents after pH value regulates, adds boron selective ion exchange
Resin, ion exchange resin uses the one in macropore polystyrene resin (ps) D564, Diaion CRB 02, Diaion CRB 01.
Remaining boron element in ion-exchange absorption attached salt lake bittern, ion exchange resin consumption is 6～40g (resin)/L (bittern).Wherein,
For D564 ion exchange resin preferably 6～18g/L, excellent for Diaion CRB02, Diaion CRB01 ion exchange resin
Select 30～40g/L.Ion-exchange absorption is attached complete after, through filter bittern can be separated with ion exchange resin.Boron contents in bittern
Below 5mg/L can be reduced to, the exploitation of follow-up more high-quality magnesium salts product can be carried out.
(7) ion exchange resin of absorption boron element uses the hydrochloric acid solution of 0.05～0.5mol/L to elute, and wherein the concentration of hydrochloric acid is excellent
Select 0.3～0.5mol/L；The volume of hydrochloric acid solution used is equal with processing salt lake bittern volume, for being effectively improved the exchange of boracic ion
The eluting rate of boron element on resin, makes ion exchange resin fully be regenerated, during ion exchange resin regeneration, hydrochloric acid is molten
Liquid is divided into three equal parts, 3 equal portions can substep, continuously ion exchange resin is eluted, can be effectively improved to boracic ion friendship
Change the eluting rate of boron on resin, make ion exchange resin sufficiently be regenerated.Ion exchange to absorption boron element the most continuously
Resin carries out eluting, filtering, until desorption process completes, obtains the boracic aqueous phase that Boron contents is 41.6～277.9mg/L, through steaming
Send out crystallization and obtain boric acid product, or re-start the attached combined separation of extraction-ion-exchange absorption after returning the mixing of crude salt lake bittern and carry boron.
Embodiment 1
A () takes after the heavy boron of salt lake acidifying is material liquid 100mL containing magnesium salts lake bittern, and Boron contents is (with B2O3Meter) it is 10.005g/L,
PH meter records the pH value of material liquid less than 1.0.The pH value of salt lake bittern is adjusted to by the NaOH solution using 0.5mol/L
1.0。
(b) preparation mixed extractant system: take aviation kerosine 50mL, be separately added into Decanol 34mL, isooctanol 15mL, phosphorus
Acid tributyl 1mL, is thoroughly mixed, and gross mass is 81.67g, is subsequently adding 2,2,4-trimethyl-1,3-pentanediol 2.80g,
Then 2,2,4-trimethyl-1, it is 3.31% that 3-pentanediol accounts for the mass fraction of total extractant, forms hybrid extraction after being sufficiently stirred for dissolving
Agent system.
(c) with after the mixed extractant system extraction heavy boron of acidifying containing magnesium salts lake bittern, extractant (O) and salt lake bittern (W)
Volume ratio be 1:1, both incorporation times are 20 minutes, and the stratification time is about 15 minutes, extraction progression be 1 grade；Will
Boric acid in bittern is extracted in organic phase, is extracted phase；Use mannitol fractional analysis method detection raffinate phase in Boron contents (with
B2O3Meter), in raffinate phase, Boron contents is 291.4mg/L, and single-stage extraction rate is 97.08%.
(d) use pH value be 10, concentration be the NaCl aqueous solution of 5g/L as back washing agent, boracic organic phase is carried out back extraction,
Back washing agent is 3:1 with the volume ratio of boracic organic phase, and both incorporation times are 20 minutes, and the stratification time is 15 minutes, instead
Extraction progression is 3 grades, and back extraction ratio is 99.2%；Boron contents is obtained (with B after back extraction2O3Meter) it is the aqueous solution of 1.070g/L
900mL obtains borax (Na through evaporative crystallization2B4O7·10H2O)3.80g。
E pH value that () regulates raffinate phase by the NaOH solution of 1.0mol/L is 6, is subsequently adding D564 ion exchange resin 1.2g,
After agitated mixing 15 minutes, through filtering, bittern and ion exchange resin are separated, same employing mannitol fractional analysis method detection halogen
Boron contents in water, Boron contents is 9.2mg/L.Salt lake bittern through extraction and the attached combined separation of ion-exchange absorption can carry out follow-up
The more production of high-quality magnesium salts product.
F the ion exchange resin D564 of the attached boracic of () ion-exchange absorption, the hydrochloric acid using 100mL concentration to be 0.5mol/L is carried out
Wash-out, is divided into 3 parts by hydrochloric acid solution, continuously the ion exchange resin of absorption boron element is eluted, is filtered, directly respectively
Completing to desorption process, eluent cumulative volume is 100mL, and concentration is that 277.9mg/L is (with B2O3Meter) boracic aqueous phase, warp
It is 49.3mg boric acid product (H that evaporative crystallization obtains quality3BO3)；Again as ion-exchange absorption after ion exchange resin regeneration
The raffinate phase of attached dose of adsorption step (e) gained.
Embodiment 2
A () takes after the heavy boron of salt lake acidifying is material liquid 100mL containing magnesium salts lake bittern, and Boron contents is (with B2O3Meter) it is 10.005g/L,
By the NaOH solution of 5mol/L, the pH value of salt lake bittern is adjusted to 5.0.
(b) preparation mixed extractant system: take aviation kerosine 50mL, be separately added into Decanol 18mL, isooctanol 30mL, phosphorus
Acid tributyl 2mL, is thoroughly mixed, and gross mass is 80.62g, is subsequently adding 2,2,4-trimethyl-1,3-pentanediol 4.24g,
Then 2,2,4-trimethyl-1, it is 5.0% that 3-pentanediol accounts for the mass fraction of total extractant, forms hybrid extraction after being sufficiently stirred for dissolving
Agent system.
(c) with after the mixed extractant system extraction heavy boron of acidifying containing magnesium salts lake bittern, extractant (O) and salt lake bittern (W)
Volume ratio be 1:1, both incorporation times are 20 minutes, and the stratification time is about 15 minutes, extraction progression be 1 grade；Will
Boric acid in bittern is extracted in organic phase, is extracted phase；Use mannitol fractional analysis method detection raffinate phase in Boron contents (with
B2O3Meter), in raffinate phase, Boron contents is 193.2mg/L, and single-stage extraction rate is 98.07%.
(d) use pH value be 11, concentration be the NaCl aqueous solution of 50g/L as back washing agent, boracic organic phase is carried out back extraction,
Back washing agent is 3:1 with the volume ratio of boracic organic phase, and both incorporation times are 20 minutes, and the stratification time is 15 minutes, instead
Extraction progression is 3 grades, and back extraction ratio is 99.8%；Boron contents is obtained (with B after back extraction2O3Meter) it is the aqueous solution of 1.088g/L
900mL, obtains borax 3.865g through evaporative crystallization.
E pH value that () regulates raffinate phase by the NaOH solution of 5.0mol/L is 9, is subsequently adding D564 ion exchange resin 1.8g,
After agitated mixing 15 minutes, through filtering, bittern and ion exchange resin are separated, same employing mannitol fractional analysis method detection halogen
Boron contents in water, Boron contents is 3.9mg/L, and the salt lake bittern through extraction and the attached combined separation of ion-exchange absorption can carry out follow-up
The more production of high-quality magnesium salts product.
F the ion exchange resin D564 of the attached boracic of () ion-exchange absorption, the hydrochloric acid using 100mL concentration to be 0.4mol/L is washed
De-, hydrochloric acid solution is divided into 3 parts, continuously the ion exchange resin of absorption boron element is eluted, filters respectively, until
Desorption process completes, and eluent cumulative volume is 100mL, and concentration is that 183.6mg/L is (with B2O3Meter) boracic aqueous phase, through steam
Send out crystallization obtaining quality is 32.6mg boric acid product；Again as ion exchange absorbent adsorption step after ion exchange resin regeneration
The raffinate phase of (e) gained.
Embodiment 3
A () takes after the heavy boron of salt lake acidifying is material liquid 100mL containing magnesium salts lake bittern, and Boron contents is (with B2O3Meter) it is 10.005g/L,
By the NaOH solution of 2mol/L, the pH value of material liquid is adjusted to 3.0.
(b) preparation mixed extractant system: take aviation kerosine 50mL, be separately added into Decanol 30mL, isooctanol 18mL, phosphorus
Acid tributyl 2mL, is thoroughly mixed, and gross mass is 81.18g, is subsequently adding 2,2,4-trimethyl-1,3-pentanediol 3.38g,
Then 2,2,4-trimethyl-1, it is 4.0% that 3-pentanediol accounts for the mass fraction of total extractant, forms hybrid extraction after being sufficiently stirred for dissolving
Agent system.
(c) with after the mixed extractant system extraction heavy boron of acidifying containing magnesium salts lake bittern, extractant (O) and salt lake bittern (W)
Volume ratio be 3:1, both incorporation times are 20 minutes, and the stratification time is about 15 minutes, extraction progression be 2 grades；Will
Boric acid in bittern is extracted in organic phase, is extracted phase；Use mannitol fractional analysis method detection raffinate phase in Boron contents (with
B2O3Meter), in raffinate phase, Boron contents is 49.3mg/L, and extraction yield is 99.5%.
(d) use pH value be 7, concentration be the NaCl aqueous solution of 2.5g/L as back washing agent, boracic organic phase is carried out back extraction,
Back washing agent is 1:1 with the volume ratio of boracic organic phase, and both incorporation times are 20 minutes, and the stratification time is 15 minutes, instead
Extraction progression is 3 grades, and back extraction ratio is 90.44%；Boron contents is obtained (with B after back extraction2O3Meter) it is the aqueous solution of 0.500g/L
1800mL, obtains borax 3.5539g through evaporative crystallization.
E pH value that () regulates raffinate phase by the NaOH solution of 3.0mol/L is 9, is subsequently adding Diaion CRB 02 ion and hands over
Change resin 3.0g, after agitated mixing 15 minutes, through filtering by bittern and ion exchange resin separately, same use sweet dew alcoholization
Boron contents in analytic approach detection bittern, Boron contents is 4.5mg/L, old through the salt lake of extraction and the attached combined separation of ion-exchange absorption
Halogen can carry out the production of follow-up more high-quality magnesium salts product.
F the ion exchange resin Diaion CRB 02 of the attached boracic of () ion-exchange absorption uses 100mL concentration to be 0.05mol/L's
Hydrochloric acid elutes, and hydrochloric acid solution is divided into 3 parts, continuously the ion exchange resin adsorbing boron element is eluted respectively,
Filtering, until desorption process completes, eluent cumulative volume is 100mL, and concentration is that 41.6mg/L is (with B2O3Meter) boracic
Aqueous phase, obtaining quality through evaporative crystallization is 7.3mg boric acid product；After ion exchange resin regeneration again attached as ion-exchange absorption
The raffinate phase of agent adsorption step (e) gained.
Embodiment 4
A () takes after the heavy boron of salt lake acidifying is material liquid 100mL containing magnesium salts lake bittern, and Boron contents is (with B2O3Meter) it is 10.005g/L,
The NaOH solution of pH value 3mol/L of material liquid is adjusted to 2.0.
(b) preparation mixed extractant system: take aviation kerosine 50mL, be separately added into Decanol 25mL, isooctanol 24mL, phosphorus
Acid tributyl 1mL, is thoroughly mixed, and gross mass is 80.16g, is subsequently adding 2,2,4-trimethyl-1,3-pentanediol 4.0g, then
2,2,4-trimethyl-1, it is 4.75% that 3-pentanediol accounts for the mass fraction of total extractant, forms mixed extractant after being sufficiently stirred for dissolving
System.
(c) with after the mixed extractant system extraction heavy boron of acidifying containing magnesium salts lake bittern, extractant (O) and salt lake bittern (W)
Volume ratio be 2:1, both incorporation times are 20 minutes, and the stratification time is about 15 minutes, extraction progression be 2 grades；Will
Boric acid in bittern is extracted in organic phase, is extracted phase；Use mannitol fractional analysis method detection raffinate phase in Boron contents (with
B2O3Meter), in raffinate phase, Boron contents is 121.7mg/L, and extraction yield is 98.78%.
(d) use pH value be 13, concentration be the NaCl aqueous solution of 10g/L as back washing agent, boracic organic phase is carried out back extraction
Taking, back washing agent is 2:1 with the volume ratio of boracic organic phase, and both incorporation times are 20 minutes, and the stratification time is 15 minutes,
Back extraction progression is 2 grades, and back extraction ratio is 98.07%；Boron contents is obtained (with B after back extraction2O3Meter) it is the water-soluble of 0.6058g/L
Liquid 1600mL, obtains borax 3.8257g through evaporative crystallization.
E pH value that () regulates raffinate phase by the NaOH solution of 0.4mol/L is 4, is subsequently adding Diaion CRB 01 ion and hands over
Change resin 4.0g, after agitated mixing 15 minutes, through filtering by bittern and ion exchange resin separately, same use sweet dew alcoholization
Boron contents in analytic approach detection bittern, Boron contents is 8.7mg/L, old through the salt lake of extraction and the attached combined separation of ion-exchange absorption
Halogen can carry out the production of follow-up more high-quality magnesium salts product.
F hydrochloric acid that the ion exchange resin Diaion CRB 01 of the attached boracic of () ion-exchange absorption uses 100mL concentration to be 0.3mol/L
Elute, hydrochloric acid solution be divided into 3 parts, continuously the ion exchange resin of absorption boron element is eluted, filters respectively,
Until desorption process completes, eluent cumulative volume is 100mL, and concentration is that 110.9mg/L is (with B2O3Meter) boracic aqueous phase,
Obtaining quality through evaporative crystallization is 19.7mg boric acid product；Again adsorb as ion exchange absorbent after ion exchange resin regeneration
The raffinate phase of step (e) gained.
Embodiment 5
A () takes after the heavy boron of salt lake acidifying is material liquid 100mL containing magnesium salts lake bittern, and Boron contents is (with B2O3Meter) it is 10.005g/L,
The NaOH solution of pH value 1mol/L of material liquid is adjusted to 4.0.
(b) preparation mixed extractant system: take aviation kerosine 50mL, be separately added into Decanol 30mL, isooctanol 18.5mL,
Tributyl phosphate 1.5mL, is thoroughly mixed, and gross mass is 81.44g, is subsequently adding 2,2,4-trimethyl-1,3-pentanediol 0.823g,
Then 2,2,4-trimethyl-1, it is 1.0% that 3-pentanediol accounts for the mass fraction of total extractant, forms hybrid extraction after being sufficiently stirred for dissolving
Agent system.
(c) with after the mixed extractant system extraction heavy boron of acidifying containing magnesium salts lake bittern, extractant (O) and salt lake bittern (W)
Volume ratio be 1:1, both incorporation times are 20 minutes, and the stratification time is about 15 minutes, extraction progression be 3 grades；Will
Boric acid in bittern is extracted in organic phase, is extracted phase；Use mannitol fractional analysis method detection raffinate phase in Boron contents (with
B2O3Meter), in raffinate phase, Boron contents is 246.6mg/L, and extraction yield is 97.54%.
(d) use pH value be 12, concentration be the NaCl aqueous solution of 25g/L as back washing agent, boracic organic phase is carried out back extraction
Taking, back washing agent is 1:1 with the volume ratio of boracic organic phase, and both incorporation times are 20 minutes, and the stratification time is 15 minutes,
Back extraction progression is 3 grades, and back extraction ratio is 99.0%；Boron contents is obtained (with B after back extraction2O3Meter) it is the aqueous solution of 1.073g/L
900mL, obtains borax 3.8132g through evaporative crystallization.
E pH value that () regulates raffinate phase by the NaOH solution of 2.0mol/L is 7, is subsequently adding D564 ion exchange resin 0.6g,
After agitated mixing 15 minutes, through filtering, bittern and ion exchange resin are separated, same employing mannitol fractional analysis method detection halogen
Boron contents in water, Boron contents is 7.1mg/L, and the salt lake bittern through extraction and the attached combined separation of ion-exchange absorption can carry out follow-up
The more production of high-quality magnesium salts product.
F hydrochloric acid that the ion exchange resin D564 of the attached boracic of () ion-exchange absorption uses 100mL concentration to be 0.2mol/L elutes,
Hydrochloric acid solution is divided into 3 parts, continuously the ion exchange resin of absorption boron element is eluted, filters respectively, until desorption
Process completes, and eluent cumulative volume is 100mL, and concentration is that 227.5mg/L is (with B2O3Meter) boracic aqueous phase, through evaporation knot
It is 40.4mg boric acid product that crystalline substance obtains quality；Again as ion exchange absorbent adsorption step (e) after ion exchange resin regeneration
The raffinate phase of gained.
Embodiment 6
A () takes after the heavy boron of salt lake acidifying is material liquid 100mL containing magnesium salts lake bittern, and Boron contents is (with B2O3Meter) it is 10.005g/L,
By the NaOH solution of 4mol/L, the pH value of salt lake bittern is adjusted to 3.0.
(b) preparation mixed extractant system: take aviation kerosine 50mL, be separately added into Decanol 30mL, isooctanol 18mL, phosphoric acid
Tributyl 2mL, is thoroughly mixed, and gross mass is 80.72g, is subsequently adding 2,2,4-trimethyl-1,3-pentanediol 2.805g, then
2,2,4-trimethyl-1, it is 3.36% that 3-pentanediol accounts for the mass fraction of total extractant, forms mixed extractant after being sufficiently stirred for dissolving
System.
(c) with after the mixed extractant system extraction heavy boron of acidifying containing magnesium salts lake bittern, extractant (O) and salt lake bittern (W)
Volume ratio is 1:1, and both incorporation times are 20 minutes, and the stratification time is about 15 minutes, and extraction progression is 2 grades；By halogen
Boric acid in water is extracted in organic phase, is extracted phase；Use mannitol fractional analysis method detection raffinate phase in Boron contents (with
B2O3Meter), in raffinate phase, Boron contents is 46.9mg/L, and extraction yield is 99.53%.
(d) use pH value be 9, concentration be the NaCl aqueous solution of 15g/L as back washing agent, boracic organic phase is carried out back extraction,
Back washing agent is 1:1 with the volume ratio of boracic organic phase, and both incorporation times are 20 minutes, and the stratification time is 15 minutes, instead
Extraction progression is 3 grades, and back extraction ratio is 99.4%；Boron contents is obtained (with B after back extraction2O3Meter) it is the aqueous solution of 1.6497g/L
600mL, obtains borax 3.907g through evaporative crystallization.
E pH value that () regulates raffinate phase by the NaOH solution of 0.5mol/L is 8, is subsequently adding the exchange of Diaion CRB 01 ion
Resin 3.5g, after agitated mixing 15 minutes, through filtering by bittern and ion exchange resin separately, same uses sweet dew alcoholization point
Boron contents in analysis method detection bittern, Boron contents is (with B2O3Meter) it is 7.9mg/L, combine point through extraction and ion-exchange absorption are attached
From salt lake bittern can carry out the production of follow-up magnesium salts product.
F salt that the ion exchange resin Diaion CRB 01 of the attached boracic of () ion-exchange absorption uses 100mL concentration to be 0.35mol/L
Acid elutes, and hydrochloric acid solution is divided into 3 parts, respectively continuously ion exchange resin to absorption boron element elute, mistake
Filter, until desorption process completes, eluent cumulative volume is 100mL, and concentration is that 37.0mg/L is (with B2O3Meter) boron water
Phase (provides concrete content and the volume of boron), and obtaining quality through evaporative crystallization is 6.5mg boric acid product；Ion exchange resin regeneration
After again as the raffinate phase of ion exchange absorbent adsorption step (e) gained.
Embodiment 7
A () takes after the heavy boron of salt lake acidifying is material liquid 100mL containing magnesium salts lake bittern, and Boron contents is (with B2O3Meter) it is 9.530g/L,
By the NaOH solution of 2mol/L, the pH value of salt lake bittern is adjusted to 3.0.
(b) preparation mixed extractant system: take aviation kerosine 50mL, be separately added into Decanol 32mL, isooctanol 17mL, phosphorus
Acid tributyl 1mL, is thoroughly mixed, and gross mass is 81.68g, is subsequently adding 2,2,4-trimethyl-1,3-pentanediol 3.02g,
Then 2,2,4-trimethyl-1, it is 3.57% that 3-pentanediol accounts for the mass fraction of total extractant, forms hybrid extraction after being sufficiently stirred for dissolving
Agent system.
(c) with after the mixed extractant system extraction heavy boron of acidifying containing magnesium salts lake bittern, extractant (O) and salt lake bittern (W)
Volume ratio be 1:1, both incorporation times are 20 minutes, and the stratification time is about 15 minutes, extraction progression be 1 grade；Will
Boric acid in bittern is extracted in organic phase, is extracted phase；Use mannitol fractional analysis method detection raffinate phase in Boron contents (with
B2O3Meter), in raffinate phase, Boron contents is 178.0mg/L, and single-stage extraction rate is 98.13%.
(d) use pH value be 11, concentration be the NaCl aqueous solution of 5g/L as back washing agent, boracic organic phase is carried out back extraction,
Back washing agent is 2:1 with the volume ratio of boracic organic phase, and both incorporation times are 20 minutes, and the stratification time is 15 minutes, instead
Extraction progression is 2 grades, and back extraction ratio is 99.06%；Boron contents is obtained (with B after back extraction2O3Meter) it is the aqueous solution of 2.316g/L
400mL, obtains borax 3.657g through evaporative crystallization.
E pH value that () regulates raffinate phase by the NaOH solution of 0.5mol/L is 8, is subsequently adding Diaion CRB 02 ion and hands over
Change resin 3.5g, after agitated mixing 15 minutes, through filtering by bittern and ion exchange resin separately, same use sweet dew alcoholization
Boron contents in analytic approach detection bittern, Boron contents is (with B2O3Meter) it is 8.1mg/L, through extraction and the attached associating of ion-exchange absorption
The salt lake bittern separated can carry out the production of follow-up magnesium salts product.
F salt that the ion exchange resin Diaion CRB 02 of the attached boracic of () ion-exchange absorption uses 100mL concentration to be 0.5mol/L
Acid elutes, and hydrochloric acid solution is divided into 3 parts, respectively continuously ion exchange resin to absorption boron element elute, mistake
Filter, until desorption process completes, eluent cumulative volume is 100mL, and concentration is that 165mg/L is (with B2O3Meter) boracic aqueous phase
(providing concrete content and the volume of boron), obtaining quality through evaporative crystallization is 16.8mg boric acid product；Ion exchange resin regeneration
After again as the raffinate phase of ion exchange absorbent adsorption step (e) gained.
Embodiment 8
A () takes after the heavy boron of salt lake acidifying is material liquid 100mL containing magnesium salts lake bittern, and Boron contents is (with B2O3Meter) it is 7.970g/L,
By the NaOH solution of 3mol/L, the pH value of salt lake bittern is adjusted to 2.0.
(b) preparation mixed extractant system: take aviation kerosine 50mL, be separately added into Decanol 24.5mL, isooctanol 24.5mL,
Tributyl phosphate 1mL, is thoroughly mixed, and gross mass is 80.10g, is subsequently adding 2,2,4-trimethyl-1,3-pentanediol 3.00g,
Then 2,2,4-trimethyl-1, it is 3.61% that 3-pentanediol accounts for the mass fraction of total extractant, forms hybrid extraction after being sufficiently stirred for dissolving
Agent system.
(c) with after the mixed extractant system extraction heavy boron of acidifying containing magnesium salts lake bittern, extractant (O) and salt lake bittern (W)
Volume ratio is 1:1, and both incorporation times are 20 minutes, and the stratification time is about 15 minutes, and extraction progression is 2 grades；By halogen
Boric acid in water is extracted in organic phase, is extracted phase；Use mannitol fractional analysis method detection raffinate phase in Boron contents (with
B2O3Meter), in raffinate phase, Boron contents is 51.4mg/L, and extraction yield is 99.35%.
(d) use pH value be 9, concentration be the NaCl aqueous solution of 10g/L as back washing agent, boracic organic phase is carried out back extraction,
Back washing agent is 1:1 with the volume ratio of boracic organic phase, and both incorporation times are 20 minutes, and the stratification time is 15 minutes, instead
Extraction progression is 3 grades, and back extraction ratio is 99.2%；Boron contents is obtained (with B after back extraction2O3Meter) it is the aqueous solution of 1.309g/L
600mL, obtains borax 3.10g through evaporative crystallization.
E pH value that () regulates raffinate phase by the NaOH solution of 1mol/L is 7, is subsequently adding Diaion CRB 01 amberlite
Fat 3.0g, after agitated mixing 15 minutes, through filtering by bittern and ion exchange resin separately, same uses mannitol fractional analysis
Boron contents in method detection bittern, Boron contents is (with B2O3Meter) it is 9.1mg/L, through extraction and the attached combined separation of ion-exchange absorption
Salt lake bittern can carry out the production of follow-up magnesium salts product.
F hydrochloric acid that the ion exchange resin Diaion CRB 01 of the attached boracic of () ion-exchange absorption uses 100mL concentration to be 0.3mol/L
Elute, hydrochloric acid solution be divided into 3 parts, continuously the ion exchange resin of absorption boron element is eluted, filters respectively,
Until desorption process completes, eluent cumulative volume is 100mL, and concentration is that 40.5mg/L is (with B2O3Meter) boracic aqueous phase (give
Go out concrete content and the volume of boron), obtaining quality through evaporative crystallization is 7.2mg boric acid product；After ion exchange resin regeneration again
Raffinate phase as ion exchange absorbent adsorption step (e) gained.
Claims (10)
1. use that solvent extraction-ion-exchange absorption is attached combines the method carrying boron, it is characterized in that the method process includes as follows
Step:
(1) at room temperature, by the pH value of salt lake bittern after the NaOH solution heavy boron of regulation acidifying between 1～5；
(2) preparation mixed extractant system: use 2,2,4-trimethyl-1,3-pentanediol and Decanol, isooctanol
Mixed alcohol be spe medium, tributyl phosphate is conditioning agent, and aviation kerosine is solvent, formed mixed extractant
System；Wherein, aviation kerosine: Decanol: isooctanol: tributyl phosphate volume ratio=100:(36～68): (30～60):
(2～4)；2,2,4-trimethyl-1,3-pentanediol consumption accounts for the 1～5% of total extractant quality；Add 2,2,4-front three
Base-1, after 3-pentanediol, forms total extractant system after agitated abundant dissolving；
(3) by the salt lake bittern after the extraction acidifying of total extractant, total extractant system and the volume ratio of salt lake bittern
For 1:1～3:1；Extraction progression is 1～3 grade, is extracted in organic phase by the boric acid in bittern, is extracted phase；
Make in raffinate phase Boron contents with B after extraction2O3Meter is reduced to below 300mg/L；
(4) NaCl solution that the boron element in organic extraction mutually uses pH value to be 7～13 carries out back extraction, NaCl
Solution is 1:1～3:1 with the volume ratio of organic phase, and back extraction progression is 1～3 grade；Boron contents is obtained big after back extraction
The aqueous solution in 0.5g/L；
(5) Boron contents being less than to the raffinate phase of 300mg/L, the NaOH solution of employing 0.5～5mol/L will
Its pH value is adjusted to 4～9；
(6) raffinate phase less than 300mg/L of the Boron contents after pH value regulates, adds boron selective ion and hands over
Change resin；Remaining boron element in ion-exchange absorption attached salt lake bittern, ion exchange resin consumption is every liter of bittern
6～40g resins；After ion exchange resin has adsorbed, bittern can be separated with ion exchange resin through filtering,
In bittern, Boron contents is with B2O3Meter can be reduced to below 5mg/L；
(7) ion exchange resin of absorption boron element uses the hydrochloric acid solution of 0.05～0.5mol/L to elute,
Obtain the Boron contents boracic aqueous phase more than 35mg/L, obtain boric acid product through evaporative crystallization, or return to crude salt lake
Re-start the attached combined separation of extraction-ion-exchange absorption after the mixing of old halogen and carry boron.
2. the method for claim 1, is characterized in that the concentration of described step (1) NaOH solution is
0.5～5mol/L.
3. the method for claim 1, is characterized in that the concentration of described step (1) NaOH solution is
0.5～2mol/L.
4. the method for claim 1, is characterized in that the pH of described step (1) NaOH regulation salt lake bittern
It is 2～3.
5. the method for claim 1, is characterized in that described step (3) extraction progression is 1～2 grade.
6. the method for claim 1, is characterized in that the boron element in described step (4) organic extraction mutually uses
PH value be 10～11 NaCl solution carry out back extraction, in NaCl solution, the concentration of NaCl is 2.5～50g/L.
7. the method for claim 1, is characterized in that described step (5) pH value is adjusted to 7～9.
8. the method for claim 1, is characterized in that described step (6) ion exchange resin uses macropore polyphenyl
One in vinyl D564, Diaion CRB 02, Diaion CRB 01；The attached salt lake of ion-exchange absorption
Remaining boron element in old halogen, ion exchange resin consumption is 6～40g (resin)/L (bittern).
9. method as claimed in claim 8, is characterized in that for D564 ion exchange resin consumption be 6～18g/L；
It is 30～40g/L for Diaion CRB 02, Diaion CRB 01 ion exchange resin consumption.
10. the method for claim 1, is characterized in that the concentration of described step (7) hydrochloric acid solution is
0.3～0.5mol/L；The volume of hydrochloric acid solution used is equal with processing salt lake bittern volume.
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