CN109264737A - Recycling lithium and the method for producing high-purity boric acid or borax - Google Patents
Recycling lithium and the method for producing high-purity boric acid or borax Download PDFInfo
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- CN109264737A CN109264737A CN201811349966.0A CN201811349966A CN109264737A CN 109264737 A CN109264737 A CN 109264737A CN 201811349966 A CN201811349966 A CN 201811349966A CN 109264737 A CN109264737 A CN 109264737A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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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
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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
- C01B35/12—Borates
- C01B35/121—Borates of alkali metal
- C01B35/122—Sodium tetraborates; Hydrates thereof, e.g. borax
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
Abstract
A method of recycling lithium simultaneously produces high-purity boric acid or borax, comprising steps of by NamLinBxOySolution acid adding is adjusted to pH2.0-7.0, and the solution after adjustment pH is pumped into membranous system, applies pressure in the two sides of reverse osmosis membrane, forms pressure difference, part water and H in solution3BO3Low-pressure side is moved to from high-pressure side through film；On high-tension side lithium ion is enriched with, and rich lithium, poor boron brine are obtained, and low-pressure side aqueous solution is the boric acid solution containing a small amount of lithium ion.The method of the present invention, except boron technology combines, can improve lithium ion yield, and realize the comprehensive utilization of boron resource in low cost, high efficiency removal brine while boron element with Nanofiltering membrane.
Description
Technical field
The present invention relates to a kind of methods for recycling lithium and producing high-purity boric acid or borax, more particularly, to a kind of use
Hyperfiltration is from NamLinBxOyThe method for recycling lithium in solution and producing high-purity boric acid or high-purity borax.
Background technique
Boron element is the necessity that ribonucleic acid is formed, and ribonucleic acid is the important foundation component of life.Hawaii is big
Post-doctoral fellow James-the Stefansson for learning Space Agency asstrobiology research institute claims: " boron rises for life on earth
Source may be critically important, because it can make nucleic acid stability, nucleic acid is the important component of ribonucleic acid.In primordial growth traits, ribose
Nucleic acid is considered as the information precursor of DNA."
Absorption And Metabolism scientific circles in relation to boron solve insufficient, and boron is easy to absorb in diet, and largely by
Urine discharge is in conjunction with oxygen in blood, is H3BO3Or B (OH)4 -, the hydroxyl formation carboxylate of boric acid and organic compound.It is dynamic
The content of boron is very low in object and the blood of people, and related with the intake of magnesium in diet, and the content of boron is just when magnesium intake is low, in blood
Increase.Boron can be accumulated in bone, but which kind of form unclear is.
Boron is prevalent in vegetables and fruits, be maintain bone health and calcium, phosphorus, magnesium eubolism required for microelement it
One.Prevent calcium loss, pre- anti-osteoporosis from having effects that women after menopause, the shortage of boron can aggravate lacking for vitamin D
It is weary；On the other hand, boron also contributes to improving male testical sterone secretory volume, tones up the muscles, is the indispensable nutrition of sportsman
Element.Boron also improves brain function, improves the effect of respond.Although most people not boron deficiency, it is necessary to suitable by the elderly
When attention is absorbed.
The physiological function of boron has not determined, there are the obvious and different reaction occurred when two kinds of hypothesis explain boron deficiency,
And the biochemical characteristic of known boron.A kind of hypothesis is that boron is a kind of cell metabolism regulatory factors, passes through some key enzymes of Reverse transcriptase
Reaction, to control many metabolic pathways.Another kind is, boron has the function of maintaining cell membrane function stable, thus, it can be with
By adjusting the transmembrane signal or movement of modulability anion or cation, to influence film to the anti-of hormone and other Auto-regulators
It answers.
In addition, boron is the distinctive indispensable element of higher plant, and animal, fungi and bacterium do not need boron.Boron can be with trip
Sugar from state combines, and sugar is made to be easy to promote the transport of sugar across plasma membrane.The content of boron is between each organ of plant to spend highest, flower
In again with column cap and ovary highest.Boron has important influence to the reproductive process of plant, with pollen formation, germination of pollen tube and by
Essence has substantial connection.When boron deficiency, anther and filigree atrophy, pollen development are bad.Rape and wheat occur " colored and not firm " existing
As that acid heat is related with Plant Boron.Tip of a root when boron deficiency, stem apex growing point stop growing, lateral root, lateral bud largely occur, rear side
Root, the growing point of lateral bud are again dead, to form fasciation shape.The contracting fruit of the brown rot of beet, the leaf curl of potato and apple
Disease etc. is all caused by boron deficiency.
Boron is also a kind of widely used industrial chemicals mineral, mainly for the production of the various chemical combination of borax, boric acid and boron
Object and element boron are the important originals of the departments such as metallurgy, building materials, machinery, electric appliance, chemical industry, light hair, nuclear industry, medicine, agricultural
Material.
Pure boron be used as good reducing agent, oxidant, bromating agent, the admixture of organic synthesis, high voltagehigh frequency electricity and
The insulator of plasma arc, the pass-through box etc. of radar.
Boron is trace alloying element, and boron is effective neutron shielding material in conjunction with plastics or aluminium alloy；Boron steel is reacting
It is used as control rod in heap；Boron fibre is for manufacturing composite material etc.；Boron-containing additive can improve sinter in metallurgical industry
Quality reduces fusing point, reduces expansion, improves intensity hardness.Boron and its compound are also the cosolvent and smelting boron of metallurgical industry
The raw material of iron boron steel is added titanium boride, boronation lithium, nickel borides, can smelt heat-resisting special alloy；Building materials.Borate, boronation
Object is the important component of enamel, ceramics, glass, has good heat-resistant antifriction, can enhance gloss, and surface smoothness is turned up
Deng.
Boric acid, zinc borate can be used for the insulating materials of fire proofing firbre, be good fire retardants, be also applied to bleaching, mordant dyeing
Etc.；Kodalk is used for fabric bleaching.In addition, boron and its compound can be used for painting desiccant, welding compound, paper industry
Mercurous sewage-treating agent etc..
Boron is present in quartz mine as microelement, in the purifying technique of glass sand, how reduction B as far as possible
Content becomes technology key.The presence of B reduces the fusing point of quartz, and silica crucible access times obtained reduce, so that single
Crystal silicon production cost increases.
Although Chinese boron resource is abundant, boron rock product is not able to satisfy domestic economy construction demand, and boron product is a large amount of
Rely on import.
During Brine resources comprehensive utilization, especially during brine mentions lithium, the boron in brine is usually as miscellaneous
Matter is removed.Traditional brine includes: dilution salt forming method, acid adding except boron method, ion-exchange are except boron method, extraction are except boron method except boron technology
Deng.
Salt forming method: boron universal village supersaturation solubility phenomenon in evaporation process in sulfate type brine is diluted, to this
Boracic brine is diluted with water the crystallizable different types of hydrated magnesium borate salt of precipitation.The technology does not introduce externalization during mentioning boron
Medicament is learned, but the removal rate of boron is low, and is only suitable for high boric brine, except the hydrated magnesium borate salt that boron obtains samples too low, nothing
Method realizes comprehensive utilization of resources, while causing elemental lithium and other high additive value element entrainment loss during removing boron.
Acid adding removes boron method: this method is only applicable to high boric brine, forms boric acid precipitating by adding hydrochloric acid into brine
Method separate thick boric acid.The removal rate of the method boron is low, and sour consumption is big, and the boric acid purity of acquisition is poor compared with low economic value, together
The entrainment loss of Shi Zaocheng elemental lithium and other high added value elements.
Ion-exchange removes boron method: using meglumine base chelating resin using the boron in the method removal brine of ion exchange, the method
The removal of boron is thorough, still, is only applicable to low boron content brine, while soda acid consumption is high, while generating regenerative wastewater, part lithium
Element enters regenerative wastewater with boron element, results in waste of resources.
Extraction removes boron method: boron is removed using extraction, the removal rate of boron is higher, but organic solvent enters in raffinate brine,
The organic solvent pollution and organic solvent security risk for causing brine bring biggish environmental protection and security burden.It is organic molten simultaneously
Agent enters in brine, brings larger limitation (not being available membrane technology, ion-exchange technology etc.) to later separation extraction.
Therefore, in order to solve many insufficient and defects of the above-mentioned prior art, it is necessary to study a kind of recycling lithium and produce
The method of high-purity boric acid or borax.
Summary of the invention
The present invention is completed in view of at least one above problem, hyperfiltration of the present invention is from NamLinBxOy
The method for recycling lithium in solution and producing high-purity boric acid or high-purity borax, separates boron element with a kind of nano filtering process from brine
Method (such as method disclosed in Chinese patent ZL201811145162.9, the content of the patent document is by reference to reference
It is integrated in the present invention) it combines, B is formed under weakly alkaline environment using boron elementxOy n-High-valence anion, using nanofiltration
Film realizes retention boron element and the low price salt such as lithium chloride, sodium chloride penetrates the separation that nanofiltration membrane realizes lithium chloride and boron, acquisition
High-pressure side trapped fluid NamLinBxOySolution allows boron element with H under mildly acidic conditions by adjusting pH3BO3Form through anti-
Permeable membrane, for producing high-purity boric acid or borax, and its high liquid side trapped fluid is the poor B solution of rich lithium, and recovery is used for carbon
The productions such as sour lithium, lithium hydroxide.Two kinds of technologies combine, and have a wide range of application, and lithium ion high income, boron removal rate are high, acid
Alkali consumption is low, at low cost, safety and environmental protection, while can realize that the high integrity of resource utilizes with high-purity borax or boric acid.
According to an aspect of the present invention, a kind of hyperfiltration is provided from NamLinBxOyLithium is recycled in solution and is produced high-purity
The method for spending boric acid or high-purity borax, includes the following steps:
A. by NamLinBxOySolution acid adding is adjusted to pH2.0-7.0；
B. it by the solution after adjustment pH, is pumped into membranous system, applies pressure in the two sides of reverse osmosis membrane, form pressure difference,
Part water and H in solution3BO3Low-pressure side is moved to from high-pressure side through film；
C. on high-tension side lithium ion is enriched with, and obtains rich lithium, poor boron brine；
D. low-pressure side aqueous solution is the boric acid solution containing a small amount of lithium ion；
Wherein, the NamLinBxOySolution, the content of B element are 100-15000ppm, and the content of lithium ion is 30-
10000ppm。。
According to a further aspect of the invention, the NamLinBxOyIn solution include chloride ion, sulfate radical, sodium ion, lithium from
Son, H3BO3And BxOy n-。
According to a further aspect of the invention, the NamLinBxOySolution acid adding is adjusted to pH2.0-7.0, acid packet used
Include hydrochloric acid or sulfuric acid.
According to a further aspect of the invention, pure water, part water and H in solution are added in the concentrate side of reverse osmosis membrane3BO3
Low-pressure side is moved to from high-pressure side through film；By constantly adding pure water, the on high-tension side H of reverse osmosis membrane3BO3Constantly is diluted and passed through
It crosses film and moves to low-pressure side to realize the separation of lithium and boron.
According to a further aspect of the invention, the boric acid solution containing a small amount of lithium ion that reverse osmosis membrane low-pressure side obtains is using anti-
Permeable membrane carries out the second-order separation, and two-pass reverse osmosis high-pressure side concentrate returns and Na described in step amLinBxOySolution is mixed
It closes, low-pressure side filtrate is high-purity boric acid solution, while promoting the lithium ion rate of recovery, obtains high-purity boric acid solution.
According to a further aspect of the invention, the poor boron brine recycling of the rich lithium that reverse osmosis membrane high-pressure side obtains is used for lithium carbonate or hydrogen
The production of lithia.
According to a further aspect of the invention, the boric acid solution that reverse osmosis membrane low-pressure side obtains in the second-order separation is dense by evaporating
Contracting, crystallization obtain high-purity boric acid, and method of evaporating includes the solarization of salt pan width or multiple-effect evaporation.
According to a further aspect of the invention, the boric acid solution that reverse osmosis membrane low-pressure side obtains in secondary separation passes through addition hydrogen-oxygen
Change sodium, adjust pH8.0-10.0, obtains NamBxOySolution；NamBxOySolution is filtered using at least one level reverse osmosis membrane, high
Pressure side is high concentration NamBxOySolution, low-pressure side are that pure water can be back to use in production technology；On high-tension side high concentration NamBxOy
Solution adjusts pH9.5-10.0 by being concentrated by evaporation, and crystallization obtains Na2B4O7·10H2O crystal.
According to a further aspect of the invention, into the Na of reverse osmosis membranemLinBxOyThe temperature of solution is 0-100 DEG C.
According to a further aspect of the invention, the pressure difference is less than or equal to 100bar, and the material of reverse osmosis membrane includes acetic acid fibre
Dimension element and its derivative, aromatic polyamide, polyimides, polysulfones, polyether sulfone, poly- piperazine, polyethylene or polypropylene.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is for producing high-purity boric acid or borax, and its high liquid side trapped fluid is the poor B solution of rich lithium, recovery set
With for productions such as lithium carbonate, lithium hydroxides.Have a wide range of application, lithium ion high income, boron removal rate are high, soda acid consumption
It is low, at low cost, safety and environmental protection, while can realize that the high integrity of resource utilizes with high-purity borax or boric acid.
Detailed description of the invention
Fig. 1 is a kind of recycling lithium of preferred embodiment and to produce the method signal of high-purity boric acid or borax according to the present invention
Figure.
Specific embodiment
With reference to the accompanying drawing, preferred forms of the invention, specific implementation here are described by preferred embodiment
Mode is to explain the present invention in detail, should not be construed as limiting the invention, and is not departing from spirit and reality of the invention
In the case where matter range, various changes and modifications can be made, these should all be included within protection scope of the present invention.
Embodiment 1
Referring to Fig. 1, the present invention provides a kind of hyperfiltrationes from NamLinBxOyLithium is recycled in solution and produces high-purity boron
The method of acid or high-purity borax, includes the following steps:
A. by NamLinBxOySolution acid adding is adjusted to pH2.0-7.0；
B. it by the solution after adjustment pH, is pumped into membranous system, applies pressure in the two sides of reverse osmosis membrane, form pressure difference,
Part water and H in solution3BO3Low-pressure side is moved to from high-pressure side through film；
C. on high-tension side lithium ion is enriched with, and obtains rich lithium, poor boron brine；
D. low-pressure side aqueous solution is the boric acid solution containing a small amount of lithium ion；
Wherein, the NamLinBxOySolution, the content of B element are 100-15000ppm, and the content of lithium ion is 30-
10000ppm。
Preferably, the NamLinBxOyIt include chloride ion, sulfate radical, sodium ion, lithium ion, H in solution3BO3With
BxOy n-。
Preferably, the NamLinBxOySolution acid adding is adjusted to pH2.0-7.0, and acid used includes hydrochloric acid or sulfuric acid.
Preferably, pure water, part water and H in solution are added in the concentrate side of reverse osmosis membrane3BO3From high-pressure side through film
Move to low-pressure side；By constantly adding pure water, the on high-tension side H of reverse osmosis membrane3BO3It is constantly diluted and is moved to by film low
Pressure side is to realize the separation of lithium and boron.
Preferably, the boric acid solution containing a small amount of lithium ion that reverse osmosis membrane low-pressure side obtains carries out two using reverse osmosis membrane
Grade separation, two-pass reverse osmosis high-pressure side concentrate return and Na described in step amLinBxOySolution mixing, low-pressure side filtrate
High-purity boric acid solution is obtained while promoting the lithium ion rate of recovery for high-purity boric acid solution.
Preferably, life of the poor boron brine recycling of the rich lithium that reverse osmosis membrane high-pressure side obtains for lithium carbonate or lithium hydroxide
It produces.
Preferably, the boric acid solution that reverse osmosis membrane low-pressure side obtains in the second-order separation is by being concentrated by evaporation, crystallization acquisition is high
Purity boric acid, method of evaporating include the solarization of salt pan width or multiple-effect evaporation.
Preferably, the boric acid solution that reverse osmosis membrane low-pressure side obtains in secondary separation passes through addition sodium hydroxide, adjustment
PH8.0-10.0 obtains NamBxOySolution；NamBxOySolution is filtered using at least one level reverse osmosis membrane, and high-pressure side is highly concentrated
Spend NamBxOySolution, low-pressure side are that pure water can be back to use in production technology；On high-tension side high concentration NamBxOySolution passes through steaming
Hair concentration, and pH9.5-10.0 is adjusted, crystallization obtains Na2B4O7·10H2O crystal.
Preferably, into the Na of reverse osmosis membranemLinBxOyThe temperature of solution is 0-100 DEG C.
Preferably, the pressure difference is less than or equal to 100bar, and the material of reverse osmosis membrane includes cellulose acetate and its derivative
Object, aromatic polyamide, polyimides, polysulfones, polyether sulfone, poly- piperazine, polyethylene or polypropylene.
The present invention is for producing high-purity boric acid or borax, and its high liquid side trapped fluid is the poor B solution of rich lithium, recovery set
With for productions such as lithium carbonate, lithium hydroxides.Have a wide range of application, lithium ion high income, boron removal rate are high, soda acid consumption
It is low, at low cost, safety and environmental protection, while can realize that the high integrity of resource utilizes with high-purity borax or boric acid.
Embodiment 2
Preferably, it additionally provides a kind of from NamLinBxOyLithium is recycled in solution and produces high-purity boric acid or high-purity boron
The method of sand.Specific step is as follows for this method:
A) acid is added into feed brine, adjustment pH is 2-7；
B) Na of pH will be adjustedmLinBxOySolution is pumped into primary reverse osmosis system, the two of reverse osmosis membrane
Side applies pressure, forms pressure difference, obtains the poor boron brine of the rich lithium of trapped fluid 1 and 1 boric acid solution of filtrate；
C) the rich poor boron brine of lithium of trapped fluid 1 is dialysed using pure water, obtains the poor boron brine of the rich lithium of trapped fluid 2 and filtrate
2 boric acid solutions；
D) filtrate 1,2 boric acid solution of filtrate are subjected to secondary filtration using reverse osmosis membrane, obtain trapped fluid 3 and filtrate 3 is high
Pure boric acid solution；；
E) trapped fluid 3 and b) step are adjusted to the Na of pHmLinBxOySolution mixing；
F) 3 high-purity boracic acid solution of filtrate enters the solarization of salt pan width, and condensing crystallizing during width shines obtains high-purity boric acid and produces
Product.
Preferably, step f) is replaced are as follows: 3 high-purity boracic acid solution of filtrate adjusts pH using sodium hydroxide, obtains more boric acid
Sodium solution；
More dobell's solutions are filtered using reverse osmosis membrane, obtain more than the 4 dobell's solution concentrates of trapped fluid and filter
4 pure water of liquid；
More than 4 dobell's solutions of trapped fluid are subjected to four-effect evaporation and adjust evaporation concentrated solution pH9.5-10.0, crystallization obtains
High-purity borax.
Preferably, the NamLinBxOySolution, lithium ion content 3000ppm, sodium ions content 2000ppm, boron content
6000ppm, brine pH10.0, brine temperature are 35 DEG C.
Preferably, lithium ion content 6000ppm in the poor boron brine of the rich lithium of trapped fluid 1, sodium ions content 4000ppm, boron contain
Measure 9000ppm；Lithium ion content 90ppm, sodium ions content 60ppm, boron content 3000ppm in 1 boric acid solution of filtrate.
Preferably, lithium ion content 6750ppm in the poor boron brine of the rich lithium of trapped fluid 2, sodium ions content 4500ppm, boron contain
Measure 1000ppm；Lithium ion content 110ppm, sodium ions content 75ppm, boron content 2000ppm in 2 boric acid solution of filtrate.
Preferably, lithium ion content 3000ppm in trapped fluid 3, sodium ions content 2000ppm, boron content 5700ppm；It cuts
Stay lithium ion content 3ppm, sodium ions content 2ppm, boron content 1950ppm in 3 high-purity boracic acid solution of liquid.
Embodiment 3
Preferably, a kind of Na is additionally providedmLinBxOySolution, lithium ion content 3000ppm, sodium ions content 2000ppm,
Boron content 6000ppm, brine pH10.0, brine temperature are 35 DEG C.
Preferably, the recycling lithium and the method for producing high-purity boric acid or high-purity borax, include the following steps:
A) hydrochloric acid is added into feed brine, adjustment pH is 4.0；
G) Na of pH will be adjustedmLinBxOySolution is pumped into primary reverse osmosis system, the two of reverse osmosis membrane
Side applies pressure, forms pressure difference, and control both sides differential pressure of membrane is 60bar, and control brine temperature is 27 DEG C；Obtain the rich lithium of trapped fluid 1
1 boric acid solution of poor boron brine and filtrate；
H) lithium ion content 6000ppm in the poor boron brine of the rich lithium of trapped fluid 1, sodium ions content 4000ppm, boron content
9000ppm；Lithium ion content 90ppm, sodium ions content 60ppm, boron content 3000ppm in 1 boric acid solution of filtrate；
I) the rich poor boron brine of lithium of trapped fluid 1 is dialysed using pure water, controlling reverse osmosis both sides differential pressure of membrane is 60bar,
Controlling brine temperature is 27 degree, obtains the poor boron brine of the rich lithium of trapped fluid 2 and 2 boric acid solution of filtrate；
J) lithium ion content 6750ppm in the poor boron brine of the rich lithium of trapped fluid 2, sodium ions content 4500ppm, boron content
1000ppm；Lithium ion content 110ppm, sodium ions content 75ppm, boron content 2000ppm in 2 boric acid solution of filtrate；
K) filtrate 1,2 boric acid solution of filtrate are subjected to secondary filtration using reverse osmosis membrane, control both sides differential pressure of membrane is
40bar, control brine temperature are 30 DEG C, obtain trapped fluid 3 and 3 high-purity boracic acid solution 3 of filtrate；
L) lithium ion content 3000ppm in trapped fluid 3, sodium ions content 2000ppm, boron content 5700ppm；Trapped fluid 3
Lithium ion content 3ppm in high-purity boracic acid solution, sodium ions content 2ppm, boron content 1950ppm；
M) by trapped fluid 3 and the aforementioned Na for adjusting pHmLinBxOySolution mixing；
N) 3 high-purity boracic acid solution of filtrate enters the solarization of salt pan width, and condensing crystallizing during width shines obtains high-purity boric acid and produces
Product.
Embodiment 4
Preferably, a kind of Na is additionally providedmLinBxOySolution, lithium ion content 2000ppm, sodium ions content 1000ppm,
Boron content 4000ppm, brine pH9.5, brine temperature are 45 DEG C.
Preferably, the recycling lithium and the method for producing high-purity boric acid or high-purity borax, include the following steps:
B) hydrochloric acid is added into feed brine, adjustment pH is 4.2；
C) Na of pH will be adjustedmLinBxOySolution is pumped into primary reverse osmosis system, the two of reverse osmosis membrane
Side applies pressure, forms pressure difference, and control both sides differential pressure of membrane is 70bar, and control brine temperature is 30 DEG C；Obtain the rich lithium of trapped fluid 1
1 boric acid solution of poor boron brine and filtrate；
D) lithium ion content 7000ppm in the poor boron brine of the rich lithium of concentrate 1, sodium ions content 3500ppm, boron content
8400ppm；Lithium ion content 50ppm, sodium ions content 25ppm, boron content 2200ppm in 1 boric acid solution of filtrate；
E) trapped fluid 1 is dialysed using pure water, controlling reverse osmosis both sides differential pressure of membrane is 70bar, controls brine temperature
It is 32 degree, obtains the poor boron brine of the rich lithium of trapped fluid 2 and 2 boric acid solution of filtrate；
F) lithium ion content 7500ppm in the poor boron brine of the rich lithium of trapped fluid 2, sodium ions content 4800ppm, boron content
700ppm；Lithium ion content 80ppm in boric acid solution 2, sodium ions content 40ppm, boron content 1500ppm；
G) filtrate 1,2 boric acid solution of filtrate are subjected to secondary filtration using reverse osmosis membrane, control both sides differential pressure of membrane is
40bar, control brine temperature are 35 degree, obtain trapped fluid 3 and 3 high-purity boracic acid solution of filtrate；
H) lithium ion content 2000ppm in trapped fluid 3, sodium ions content 1000ppm, boron content 4100ppm；Filtrate 3 is high
Lithium ion content 2.5ppm in pure boric acid solution, sodium ions content 1.5ppm, boron content 1400ppm；
I) trapped fluid 3 and b) step are adjusted to the Na of pHmLinBxOySolution mixing；
J) 3 high-purity boracic acid solution of filtrate adjusts pH to 9.3 using sodium hydroxide, obtains more dobell's solutions；
K) more dobell's solutions are filtered using reverse osmosis membrane, obtain more than the 4 dobell's solution concentrates of trapped fluid and
4 pure water of filtrate；
L) more than 4 dobell's solutions of trapped fluid are subjected to four-effect evaporation and adjust evaporation concentrated solution pH9.5-10.0, crystallization obtains
Obtain high-purity borax.
Embodiment 5
Preferably, a kind of NamLinBxOySolution, lithium ion content 4000ppm, sodium ions content 2500ppm, boron content
8000ppm, brine pH10.0, brine temperature are 50 DEG C.Specific step is as follows for this method:
A) hydrochloric acid is added into feed brine, adjustment pH is 3.5；
B) Na of pH will be adjustedmLinBxOySolution is pumped into primary reverse osmosis system, the two of reverse osmosis membrane
Side applies pressure, forms pressure difference, and control both sides differential pressure of membrane is 85bar, and control brine temperature is 60 DEG C；Obtain the rich lithium of trapped fluid 1
1 boric acid solution of poor boron brine and filtrate；
C) lithium ion content 8500ppm in the poor boron brine of the rich lithium of concentrate 1, sodium ions content 5300ppm, boron content
12000ppm；Lithium ion content 125ppm, sodium ions content 70ppm, boron content 4200ppm in 1 boric acid solution of filtrate；
D) trapped fluid 1 is dialysed using pure water, controlling reverse osmosis both sides differential pressure of membrane is 85bar, controls brine temperature
It is 60 DEG C, obtains the poor boron brine of the rich lithium of trapped fluid 2 and 2 boric acid solution of filtrate；
E) lithium ion content 9000ppm in the poor boron brine of the rich lithium of trapped fluid 2, sodium ions content 5700ppm, boron content
1100ppm；Lithium ion content 150ppm in boric acid solution 2, sodium ions content 85ppm, boron content 2700ppm；
F) filtrate 1,2 boric acid solution of filtrate are subjected to secondary filtration using reverse osmosis membrane, control both sides differential pressure of membrane is
50bar, control brine temperature are 37 DEG C, obtain trapped fluid 3 and 3 high-purity boracic acid solution of filtrate；
G) lithium ion content 4000ppm in trapped fluid 3, sodium ions content 2500ppm, boron content 7500ppm；Filtrate 3 is high
Lithium ion content 4ppm in pure boric acid solution, sodium ions content 2.5ppm, boron content 2800ppm；
H) trapped fluid 3 and b) step are adjusted to the Na of pHmLinBxOySolution mixing；
I) 3 high-purity boracic acid solution of filtrate adjusts pH to 9.5 using sodium hydroxide, obtains more dobell's solutions；
J) more dobell's solutions are filtered using reverse osmosis membrane, obtain more than the 4 dobell's solution concentrates of trapped fluid and
4 pure water of filtrate；
More than 5 dobell's solutions of trapped fluid are subjected to four-effect evaporation and adjust evaporation concentrated solution pH9.5-10.0, crystallization obtains
High-purity borax.
In conclusion the beneficial effects of the present invention are:
The present invention is for producing high-purity boric acid or borax, and its high liquid side trapped fluid is the poor B solution of rich lithium, recovery set
With for productions such as lithium carbonate, lithium hydroxides.Have a wide range of application, lithium ion high income, boron removal rate are high, soda acid consumption
It is low, at low cost, safety and environmental protection, while can realize that the high integrity of resource utilizes with high-purity borax or boric acid.In addition, of the invention
With Nanofiltering membrane except boron technology combines, it can improve lithium ion in low cost, high efficiency removal brine while boron element and receive
Rate, and realize the comprehensive utilization of boron resource.
The present invention is not limited to above-mentioned specific embodiments.It is understood that not departing from spirit and substance of the present invention model
In the case where enclosing, various changes and modifications can be made, these should all be included within protection scope of the present invention.
Claims (10)
1. a kind of hyperfiltration is from NamLinBxOyThe method for recycling lithium in solution and producing high-purity boric acid or high-purity borax, packet
Include following step:
A. by NamLinBxOySolution acid adding is adjusted to pH2.0-7.0；
B. it by the solution after adjustment pH, is pumped into membranous system, applies pressure in the two sides of reverse osmosis membrane, form pressure difference, solution
In part water and H3BO3Low-pressure side is moved to from high-pressure side through film；
C. on high-tension side lithium ion is enriched with, and obtains rich lithium, poor boron brine；
D. low-pressure side aqueous solution is the boric acid solution containing a small amount of lithium ion；
Wherein, the NamLinBxOySolution, the content of B element are 100-15000ppm, and the content of lithium ion is 30-
10000ppm。
2. method according to claim 1, it is characterised in that the NamLinBxOyIt include chloride ion, sulfuric acid in solution
Root, sodium ion, lithium ion, H3BO3And BxOy n-。
3. method according to claim 1, it is characterised in that the NamLinBxOySolution acid adding is adjusted to pH2.0-
7.0, acid used includes hydrochloric acid or sulfuric acid.
4. method according to claim 1, it is characterised in that in the concentrate side of reverse osmosis membrane addition pure water, solution
Part water and H3BO3Low-pressure side is moved to from high-pressure side through film；By constantly adding pure water, the on high-tension side H of reverse osmosis membrane3BO3
It is constantly diluted and moves to low-pressure side by film to realize the separation of lithium and boron.
5. method according to claim 1, it is characterised in that reverse osmosis membrane low-pressure side obtained contains a small amount of lithium ion
Boric acid solution using reverse osmosis membrane carry out the second-order separation, two-pass reverse osmosis high-pressure side concentrate return with step a described in
NamLinBxOySolution mixing, low-pressure side filtrate is high-purity boric acid solution, while promoting the lithium ion rate of recovery, is obtained high
Purity boric acid solution.
6. according to the method described in claim 1, it is characterized in that the poor boron brine recycling of rich lithium that reverse osmosis membrane high-pressure side obtains
Production for lithium carbonate or lithium hydroxide.
7. according to the method described in claim 1, it is characterized in that the boric acid that reverse osmosis membrane low-pressure side obtains in the second-order separation is molten
Liquid is by being concentrated by evaporation, crystallization obtains high-purity boric acid, and method of evaporating includes the solarization of salt pan width or multiple-effect evaporation.
8. according to the method described in claim 1, it is characterized in that the boric acid that reverse osmosis membrane low-pressure side obtains in secondary separation is molten
Liquid adjusts pH8.0-10.0 by addition sodium hydroxide, obtains NamBxOySolution；NamBxOySolution is reverse osmosis using at least one level
Film is filtered, and high-pressure side is high concentration NamBxOySolution, low-pressure side are that pure water can be back to use in production technology；It is on high-tension side
High concentration NamBxOySolution adjusts pH9.5-10.0 by being concentrated by evaporation, and crystallization obtains Na2B4O7·10H2O crystal.
9. according to the method described in claim 1, it is characterized in that into reverse osmosis membrane NamLinBxOyThe temperature of solution is 0-
100℃。
10. according to claim 1, method described in 5 or 8, it is characterised in that the pressure difference be less than or equal to 100bar, it is reverse osmosis
The material of film includes cellulose acetate and its derivative, aromatic polyamide, polyimides, polysulfones, polyether sulfone, poly- piperazine, gathers
Ethylene or polypropylene.
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