CN109678167A - A method of boric acid is produced from lithium borate waste solution is mentioned - Google Patents
A method of boric acid is produced from lithium borate waste solution is mentioned Download PDFInfo
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- CN109678167A CN109678167A CN201910163180.8A CN201910163180A CN109678167A CN 109678167 A CN109678167 A CN 109678167A CN 201910163180 A CN201910163180 A CN 201910163180A CN 109678167 A CN109678167 A CN 109678167A
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- boric acid
- waste solution
- lithium borate
- borate waste
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention provides a kind of from the method for recycling boric acid in lithium borate waste solution is proposed, and belongs to the technical field of production of inorganic technique.The present invention will mention lithium borate waste solution and adjust pH value to 3.5~4.5 and then drain into analysis boron salt field and be evaporated crystallization, and water evaporation comes out, formation boric acid crystal and mother liquid of boric acid；Boric acid crystal produces analysis boron salt field with mother liquid of boric acid in the form of mixing boric acid feed liquid, after dense thickening and deposition, obtains boric acid magma and supernatant；Supernatant is back to analysis boron salt field and carries out further evaporative crystallization；Boric acid magma is separated by solid-liquid separation, and boric acid and boron-bearing liquid are obtained；Boron-bearing liquid is back to analysis boron salt field and carries out further evaporative crystallization.The mass percentage for the boric acid that the present invention obtains is 87~98%, is efficiently utilized so that mentioning lithium borate waste solution, realizes the efficient utilization of outlet waste water containing boron；And this method has many advantages, such as that pollution is small, low energy consumption, high income, thick boron are high-quality.
Description
Technical field
The present invention relates to the technical fields of production of inorganic technique, more particularly to one kind to produce boric acid from lithium borate waste solution is mentioned
Method.
Background technique
The current boric acid production almost all in the whole world is produced using solid crude boron stone, needs to consume in process of production a large amount of
Strong acid, not only operating condition is poor in production process, and the waste liquid of subsequent generation, fixed-end forces not only technical difficulty it is big but also
Investment is big, causes biggish obstacle to environmental and ecological protection, gives manufacturing enterprise also bring certain economic impact.
China's boron rock proved reserves (folding B2O3) about 50,000,000 tons, wherein most is boromagnesite and boron magnesium iron mixed ore,
About 20,000,000 tons of another part (folding B2O3) it is bittern type and salt lake solid crude boron stone, it is mainly distributed on the modern times in Qinghai, Tibet
In salt lake.The all solid minerals of Liaoning boron resource；The 64% of national reserves is accounted for, yield accounts for national boron product yield
88.8%, it is the main boron rock in China and boron production processing base.Since last century the fifties since exploitation production,
As the exploitation of nearly half a century is processed, close to the situation of resource exhaustion.
Lithium resource and the reserves of boron resource are larger in China's salt lake bittern and oil field water, but the two is in salt lake bittern and oil field
Lower 0.1~3%, pH:6~7 of percentage composition in water, direct development difficulty are larger.In recent years, in China and full generation
Boundary also promotes the country and mentions the quick of lithium technology from salt lake bittern and oil field water with the fast development of electric car industry
Development, main production technology have resin adsorption method, extraction, electroosmose process, embrane method etc., and have industrial production application real
Example.
Salt lake bittern and oil field water are mentioned for lithium, boron is foreign ion, in order to guarantee the quality of lithium product, it is necessary to
During mentioning lithium, first boron element is discharged from salt lake bittern and oil field water in the form of mentioning lithium borate waste solution lithium processing system
System, so that it is guaranteed that the quality of lithium product.In order to improve the comprehensive yield of lithium and the removal efficiency of boron, can all be incited somebody to action in technical process
Boron carries out certain enrichment then discharge system in the form of mentioning lithium borate waste solution.If not to this part mention lithium borate waste solution into
The exploitation of row reasonable utilization, will not only cause the loss of boron resource, but also be difficult to solve the poverty-stricken office of solid boron rock exploitation totally
Face.This part mentions the mass percentage of boric acid in lithium borate waste solution in 0.2~6%, pH:1~6.5, if to it using strong
Evaporative crystallization processed is there is only the excessive cost of energy consumption is excessively high, and the problem of will cause equipment heavy corrosion, and use salt pan from
Right evaporative crystallization, if can exist without pH adjustment in advance, acid gas evaporation is poor to the pollution of environment and product quality to be asked
It inscribes, the mass percentage of boric acid is generally 70~85% in thick boric acid.
The scientific worker that this great difficult problem is always boron field how is scientifically and rationally solved to seek assiduously effort
Direction.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of from the method for mentioning lithium borate waste solution production boric acid.The present invention
The boron high efficiente callback that can will mention in lithium borate waste solution of method, not only environmental protection and energy saving but also good product quality comprehensive yield is high.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of from proposing the method for preparing boric acid in lithium borate waste solution, comprising the following steps:
(1) pH value for mentioning lithium borate waste solution is adjusted to 3.5~4.5, obtains pretreatment and mentions lithium borate waste solution；
(2) pretreatment that the step (1) obtains is mentioned into lithium borate waste solution and is discharged into analysis boron salt field, carry out natural evaporation knot
Crystalline substance obtains high quality boric acid crystal and mother liquid of boric acid；
(3) the boric acid crystal and part mother liquid of boric acid obtained the step (2) in the form of mixture boric acid feed liquid from
After analysis boron salt field is produced, dense thickening, the supernatant of dense thickening feed liquid deposited the boric acid magma for forming lower layer and upper layer are carried out
Liquid；
(4) the boric acid magma in the step (3) is separated by solid-liquid separation, obtains boric acid and boron-bearing liquid.
Preferably, the pH value that lithium borate waste solution is mentioned in the step (1) is 0.1~6.5.
Preferably, the source that lithium borate waste solution is mentioned in the step (1) includes that salt lake bittern proposes lithium process or oil field water mentions
Lithium process.
Preferably, adjust in the step (1) mention reagent used in lithium borate waste solution pH value include quick lime, lime stone,
One of magnesia, magnesium sulfate, sodium hydroxide, sodium carbonate, sodium bicarbonate, hydrochloric acid or sulfuric acid are a variety of.
Preferably, analysis boron salt field is piled up by clay in the step (2), and bottom is laid with uvioresistant barrier plastic film
Material.
Preferably, analysis boron salt Tanaka level is 1~3m in the step (2).
Preferably, the solid content of dense thickening feed liquid is 30~60% in the step (3).
It preferably, further include that the supernatant that the step (3) obtains is discharged into analysis boron salt field and is evaporated crystallization.
It preferably, further include that the boron-bearing liquid that the step (4) obtains is discharged into analysis boron salt field and is evaporated crystallization.
Preferably, the mass percentage of boric acid is 87~98% in the boric acid that the step (4) obtains.
The present invention will mention after lithium borate waste solution first adjusts pH value, carry out natural evaporation crystallization into analysis boron salt field；It will obtain
Boric acid crystal and mother liquid of boric acid through dense thickening, separation of solid and liquid, obtain the boric acid that boric acid mass percentage is 87~98%；
The boron high efficiente callback that this method can will mention in lithium borate waste solution can greatly save energy consumption using natural evaporation, adjust pH
When value can avoid natural evaporation as acid gas evaporates into atmosphere and caused by environmental pollution, and pH is in 3.5~4.5 value ranges
Interior, spontaneous nucleation can obtain large-particle monocrystal crystallization, the product quality obtained.
Detailed description of the invention
Fig. 1 is the present invention from mentioning the method flow diagram for preparing boric acid in lithium borate waste solution；
Fig. 2 is the stereoscan photograph of 1 gained boric acid of embodiment crystallization；
Fig. 3 is the stereoscan photograph of 2 gained boric acid of embodiment crystallization；
Fig. 4 is the stereoscan photograph of 3 gained boric acid of embodiment crystallization；
Fig. 5 is the stereoscan photograph of 4 gained boric acid of embodiment crystallization；
Fig. 6 is the stereoscan photograph of 5 gained boric acid of embodiment crystallization；
Fig. 7 is the stereoscan photograph of 6 gained boric acid of embodiment crystallization.
Specific embodiment
The present invention provides a kind of from proposing the method for preparing boric acid in lithium borate waste solution, comprising the following steps:
(1) pH value for mentioning lithium borate waste solution is adjusted to 3.5~4.5, obtains pretreatment and mentions lithium borate waste solution；
(2) pretreatment that the step (1) obtains is mentioned into lithium borate waste solution and is discharged into analysis boron salt field, carry out natural evaporation knot
Crystalline substance obtains high quality boric acid crystal and mother liquid of boric acid；
(3) the boric acid crystal and part mother liquid of boric acid obtained the step (2) in the form of mixture boric acid feed liquid from
After analysis boron salt field is produced, dense thickening, the supernatant of dense thickening feed liquid deposited the boric acid magma for forming lower layer and upper layer are carried out
Liquid；
(4) the boric acid magma in the step (3) is separated by solid-liquid separation, obtains boric acid and boron-bearing liquid.
The pH value for mentioning lithium borate waste solution is adjusted to 3.5~4.5 by the present invention, is obtained pretreatment and is mentioned lithium borate waste solution.
In the present invention, the source for mentioning lithium borate waste solution is preferably that salt lake bittern proposes lithium process or oil field water proposes lithium mistake
Journey.In the present invention, the mass concentration for mentioning boric acid in lithium borate waste solution is preferably 0.1~10%, and the lithium boracic that mentions gives up
The pH value of liquid is preferably 0.1~6.5.In the present invention, reagent used in lithium borate waste solution pH value is mentioned described in adjusting to preferably include
One of quick lime, lime stone, magnesia, magnesium sulfate, sodium hydroxide, sodium carbonate, sodium bicarbonate, hydrochloric acid and sulfuric acid are more
Kind.In the present invention, it is 3.5~4.5, preferably 4.0 that the pretreatment, which proposes the pH value of lithium borate waste solution,.
The pH value that present invention pretreatment mentions lithium borate waste solution is 3.5~4.5, so that the subsequent evaporation speed in analysis boron salt Tanaka
Degree is fast, and can reduce the corrosion to equipment and the requirement for anticorrosion to equipment and materials, avoids excessive investment waste.
Pretreatment is obtained to mention in lithium borate waste solution, the pretreatment is mentioned lithium borate waste solution and is discharged into analysis boron salt field by the present invention,
Natural evaporation crystallization is carried out, high quality boric acid monocrystalline crystal and mother liquid of boric acid are obtained.
In the present invention, the analysis boron salt field is preferably dimensioned to be 500m × 600m × 2.5m.In the present invention, the analysis
Boron salt field is preferably piled up by clay, and analysis boron salt field bottom is laid with uvioresistant barrier plastic membrane material.The present invention is to described
The source of uvioresistant barrier plastic membrane material does not have special restriction, is using commercial product well known to those skilled in the art
It can.
Pretreatment of the invention mentions lithium borate waste solution and utilizes the natural energy sources such as solar energy, wind energy, nature in analysis boron salt Tanaka
The hypersaturated state that part fresh water reaches boric acid is evaporated, boric acid crystal is formed and is precipitated in salt pan bottom, while being accompanied by boric acid
Mother liquor is formed.
After obtaining boric acid crystal and mother liquid of boric acid, the present invention is by the boric acid crystal and part mother liquid of boric acid with mixture boron
After the form of sour feed liquid is produced from analysis boron salt field, dense thickening is carried out, the dense deposited boric acid for forming lower layer of thickening feed liquid is brilliant
The supernatant of slurry and upper layer.
In the present invention, the branch mode of the boric acid feed liquid is preferably to use special-purpose machinery that the boric acid of salt pan bottom is brilliant
Body and part mother liquid of boric acid are shifted in the form of boric acid feed liquid；The special-purpose machinery preferably includes Ship, sand dredger or crawler belt
Ore pulp harvests machinery etc..In the present invention, the solid content of the boric acid feed liquid is preferably 5~45%, further preferably 20~
40%, more preferably 25~35%.The amount that the present invention accounts for mother liquid of boric acid to the part mother liquid of boric acid does not limit, as long as can
Make solid content 5~45% in boric acid feed liquid.In the present invention, it is collected since boric acid crystal is difficult directly to acquire,
Boric acid crystal and part mother liquid of boric acid are shifted in the form of boric acid slurries.
In the present invention, device used in the dense thickening is preferably concentrator.In the present invention, the dense thickening
The solid content of feed liquid is preferably 30~60%, and further preferably 40~50%, more preferably 45%.The present invention is to described dense
The time that thickening fluid is stood does not have special restriction, as long as feed liquid is enable to deposit, on boric acid magma and the upper layer for forming lower layer
Supernatant.Upper layer supernatant is preferably discharged into analysis boron salt field and is evaporated crystallization by the present invention, realizes that further boron returns
It receives.In the present invention, the supernatant is evaporated the parameter of crystallization in analysis boron salt Tanaka and the pretreatment mentions lithium boracic and gives up
Liquid is consistent in the evaporative crystallization parameter of analysis boron salt Tanaka, and details are not described herein.
After obtaining boric acid magma and supernatant, boric acid magma is separated by solid-liquid separation by the present invention, obtains boric acid and boracic liquid
Body.
In the present invention, the equipment for carrying out the separation of solid and liquid is preferably band filter, centrifuge or filter press, into one
Step is preferably centrifuge.In the present invention, the mass percentage of boric acid is preferably 87~98% in the boric acid.The present invention is excellent
Boron-bearing liquid is discharged into analysis boron salt field and is evaporated crystallization by choosing, realizes further boron recycling.In the present invention, the boracic liquid
Body is evaporated the parameter of crystallization in analysis boron salt Tanaka and the pretreatment mentions lithium borate waste solution in the evaporation knot of analysis boron salt Tanaka
Brilliant parameter is consistent, and details are not described herein.
Fig. 1 is the present invention from mentioning the method flow for preparing boric acid in lithium borate waste solution: will mention lithium borate waste solution and adjusts pH value
Analysis boron salt field is then drained into 3.5~4.5 and carries out natural evaporation crystallization, and water evaporation comes out, and forms boric acid crystal and mother liquid of boric acid；
Boric acid crystal and mother liquid of boric acid are transferred out of analysis boron salt field in the form of mixing boric acid feed liquid, after dense thickening, obtain boric acid crystalline substance
Slurry and supernatant；Supernatant is back to analysis boron salt field and carries out further evaporative crystallization；Boric acid magma is separated by solid-liquid separation, and boric acid is obtained
And boron-bearing liquid；Boron-bearing liquid is back to analysis boron salt field and carries out further evaporative crystallization.
Below with reference to embodiment to it is provided by the invention from mention boric acid is prepared in lithium borate waste solution method carry out it is detailed
Illustrate, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
By big bavin denier salt lake bittern mention lithium process generation mention lithium borate waste solution for: it is described mention lithium borate waste solution include with
The component of lower mass concentration: H3BO34.89%, MgCl20.37%, HCl 0.26%, H2O 94.48%；It is described to mention lithium boracic
The pH value of waste liquid is 1.5；
(1) pH value for mentioning lithium borate waste solution is adjusted to 4.0 using lime stone (calcium carbonate), obtains pretreatment and mentions lithium boracic
Waste liquid；
(2) pretreatment that the step (1) obtains is mentioned into lithium borate waste solution and is discharged into analysis boron salt field, institute using delivery pump device
The liquid level depth 3.0m in analysis boron salt field is stated, natural evaporation crystallizes 300 days, obtains boric acid crystal and mother liquid of boric acid；The analysis boron salt
The size in field is 20m × 20m × 3m；The analysis boron salt field is preferably piled up by clay, and analysis boron salt field bottom is laid with uvioresistant
Line barrier plastic membrane material.
(3) (solid content is about with mixture boric acid feed liquid for the boric acid crystal and part mother liquid of boric acid obtained the step (2)
Be form 15%) after the transfer of analysis boron salt field, carry out dense thickening 1.5h using concentrator, obtain dense thickening fluid (admittedly contain
Amount is about 45%)；Dense thickening fluid obtains being deposited on the boric acid magma of lower layer and the supernatant on upper layer through standing 1h；The supernatant
Liquid is back to analysis boron salt field；
(4) the boric acid magma in the step (3) is subjected to separation of solid and liquid 5min using centrifuge, obtains boric acid and boracic
Liquid；The boron-bearing liquid is back to analysis boron salt field；The boric acid crystallization is long cylindricality single crystal grain, and stereoscan photograph is such as
Shown in Fig. 2, as can be seen from Figure 2: the average particle size of gained boric acid crystallization is 1.2mm；The mass percentage of boric acid in boric acid
It is 96.5%.
Embodiment 2
By big bavin denier salt lake bittern mention lithium process generation mention lithium borate waste solution for: it is described mention lithium borate waste solution include with
The component of lower mass concentration: H3BO35.2%, MgCl20.47%, HCl 0.22%, H2O 94.11%；It is described to mention lithium boracic
The pH value of waste liquid is 1.5；
(1) pH value for mentioning lithium borate waste solution is adjusted to 4.0 using quick lime (calcium oxide), obtains pretreatment and mentions lithium boracic
Waste liquid；
(2) pretreatment that the step (1) obtains is mentioned into lithium borate waste solution and is discharged into analysis boron salt field, analysis using delivery pump device
The liquid level depth 2.5m in boron salt field, natural evaporation crystallize 300 days, obtain boric acid crystal and mother liquid of boric acid；The analysis boron salt field
Having a size of 20m × 20m × 3m；The analysis boron salt field is preferably piled up by clay, and it is anti-that analysis boron salt field bottom is laid with uvioresistant
Seep plastic film material.
(3) (solid content is about with mixture boric acid feed liquid for the boric acid crystal and part mother liquid of boric acid obtained the step (2)
Be form 25%) after the transfer of analysis boron salt field, carry out dense thickening 1.5h using concentrator, obtain dense thickening fluid (admittedly contain
Amount is about 45%)；Dense thickening fluid obtains being deposited on the boric acid magma of lower layer and the supernatant on upper layer through standing 1.0h；On described
Clear liquid is back to analysis boron salt field；
(4) the boric acid magma in the step (3) is subjected to separation of solid and liquid 5min using centrifuge, obtains boric acid and boracic
Liquid；The boron-bearing liquid is back to analysis boron salt field；The boric acid crystallization is long cylindricality single crystal grain, and stereoscan photograph is such as
Shown in Fig. 3, as can be seen from Figure 3: the average particle size of gained boric acid crystallization is 1.1mm；The mass percentage of boric acid in boric acid
It is 96.1%.
Embodiment 3
By big bavin denier salt lake bittern mention lithium process generation mention lithium borate waste solution for: it is described mention lithium borate waste solution include with
The component of lower mass concentration: H3BO35.6%, MgCl20.48%, HCl 0.28%, H2O 93.64%；It is described to mention lithium boracic
The pH value of waste liquid is 1.5；
(1) pH value for mentioning lithium borate waste solution is adjusted to 4.0 using quick lime (calcium oxide), obtains pretreatment and mentions lithium boracic
Waste liquid；
(2) pretreatment that the step (1) obtains is mentioned into lithium borate waste solution and is discharged into analysis boron salt field, analysis using delivery pump device
The liquid level depth 2.0m in boron salt field, natural evaporation crystallize 300 days, obtain boric acid crystal and mother liquid of boric acid；The analysis boron salt field
Having a size of 20m × 20m × 3m；The analysis boron salt field is preferably piled up by clay, and it is anti-that analysis boron salt field bottom is laid with uvioresistant
Seep plastic film material.
(3) the boric acid crystal and part mother liquid of boric acid obtained the step (2) is with mixture boric acid feed liquid (about solid content
About 30%) form carries out dense thickening 1.0h after the transfer of analysis boron salt field, using concentrator, obtain dense thickening fluid (Gu
45%) content is about；Dense thickening fluid obtains being deposited on the boric acid magma of lower layer and the supernatant on upper layer through standing 1.0h；It is described
Supernatant is back to analysis boron salt field；
(4) the boric acid magma in the step (3) is subjected to separation of solid and liquid 5min using centrifuge, obtains boric acid and boracic
Liquid；The boron-bearing liquid is back to analysis boron salt field；The boric acid crystallization is long cylindricality single crystal grain, and stereoscan photograph is such as
Shown in Fig. 4, as can be seen from Figure 4: the average particle size of gained boric acid crystallization is 0.8mm；The mass percentage of boric acid in boric acid
It is 94.2%.
Embodiment 4
By big bavin denier salt lake bittern mention lithium process generation mention lithium borate waste solution for: it is described mention lithium borate waste solution include with
The component of lower mass concentration: H3BO35.1%, MgCl20.39%, HCl 0.27%, H2O 94.24%；It is described to mention lithium boracic
The pH value of waste liquid is 1.5；
(1) pH value for mentioning lithium borate waste solution is adjusted to 4 using lime stone (calcium carbonate), obtaining pretreatment, to mention lithium boracic useless
Liquid；
(2) pretreatment that the step (1) obtains is mentioned into lithium borate waste solution and is discharged into analysis boron salt field, liquid using delivery pump device
Bit depth 1.5m, natural evaporation crystallize 300 days, obtain boric acid crystal and mother liquid of boric acid；It is described analysis boron salt field size be 20m ×
20m×3m；The analysis boron salt field is preferably piled up by clay, and analysis boron salt field bottom is laid with uvioresistant barrier plastic membrane material
Material；
(3) (solid content is about with mixture boric acid feed liquid for the boric acid crystal and part mother liquid of boric acid obtained the step (2)
It is form 50%) after the transfer of analysis boron salt field, carries out dense thickening 1h using concentrator, obtain dense thickening fluid (solid content
About 60%)；Dense thickening fluid obtains being deposited on the boric acid magma of lower layer and the supernatant on upper layer through standing 1h；The supernatant
It is back to analysis boron salt field；
(4) the boric acid magma in the step (3) is subjected to separation of solid and liquid 5min using centrifuge, obtains boric acid and boracic
Liquid；The boron-bearing liquid is back to analysis boron salt field；The boric acid crystallization is aciculiform and cylindricality mixed crystal, and stereoscan photograph is such as
Shown in Fig. 5, as can be seen from Figure 5: the average particle size of gained boric acid crystallization is 0.5mm, the mass percentage of boric acid in boric acid
It is 90.6%.
On the basis of this embodiment, the influence for the boric acid crystal that different borate waste solution depth obtain natural evaporation is studied,
The results are shown in Table 1.
Table 1 mentions the natural evaporation experimental data table under lithium borate waste solution different depth
Embodiment 5
For wiping your sweat salt lake bittern and mention lithium process borate waste solution (membrane process craft): tell mention lithium borate waste solution include with
The component of lower mass concentration: H3BO30.65%, MgCl20.52%, H2O 98.83%；The pH value for mentioning lithium borate waste solution
It is 6.5；
(1) pH value for mentioning lithium borate waste solution is adjusted to 4 using hydrochloric acid (HCl), obtains pretreatment and mentions lithium borate waste solution；
(2) pretreatment that the step (1) obtains is mentioned into lithium borate waste solution and is discharged into analysis boron salt field, liquid using delivery pump device
Bit depth 3.0m, natural evaporation crystallize 300 days, obtain boric acid crystal and mother liquid of boric acid；It is described analysis boron salt field size be 20m ×
20m×3m；The analysis boron salt field is preferably piled up by clay, and analysis boron salt field bottom is laid with uvioresistant barrier plastic membrane material
Material；
(3) (solid content is about with mixture boric acid feed liquid for the boric acid crystal and part mother liquid of boric acid obtained the step (2)
Be form 15%) after the transfer of analysis boron salt field, carry out dense thickening 1.5h using concentrator, obtain dense thickening fluid (admittedly contain
Amount is about 40%)；Dense thickening fluid obtains being deposited on the boric acid magma of lower layer and the supernatant on upper layer through standing 1h；The supernatant
Liquid is back to analysis boron salt field；
(4) the boric acid magma in the step (3) is subjected to separation of solid and liquid 5min using centrifuge, obtains boric acid and boracic
Liquid；The boron-bearing liquid is back to analysis boron salt field；The boric acid crystallization is cylindricality monocrystalline, stereoscan photograph such as Fig. 6 institute
Show, as can be seen from Figure 6: the average particle size of gained boric acid crystallization is 1.2mm；The mass percentage of boric acid is in boric acid
94.6%.
Embodiment 6
Using big bavin denier salt lake bittern mention lithium process generation mention lithium borate waste solution as raw material, the lithium borate waste solution that mentions includes
The component of following mass concentration: H3BO35.5%, MgCl20.45%, HCl 0.25%, H2O 93.8%；It is described to mention lithium boracic
The pH value of waste liquid is 1.5；
(1) it takes 8 parts of 250L are above-mentioned to mention lithium borate waste solution respectively, lithium borate waste solution will be mentioned respectively using lime stone (calcium carbonate)
PH value be adjusted to 1.5,2.0,3.0,3.5,4.0,4.5,5.0,6.0, obtain pretreatment mention lithium borate waste solution；
(2) pretreatment that the step (1) obtains is mentioned into lithium borate waste solution and pours into 8 0.6m × 0.6m × 0.8m appearance respectively
In device, liquid level depth 0.7m is placed in the evaporation simulator of salt pan, is evaporated 100 days, is obtained boric acid crystal and mother liquid of boric acid；Institute
Stating container is the plastic material square tube that external process is ordered, and container inner wall is laid with uvioresistant barrier plastic membrane material；
(3) supernatant that extraction raffinate after the step (2) evaporation is removed to 0.2m height about 70L in the method for siphon, obtains
Boric acid crystal and part mother liquid of boric acid, be transferred to centrifuge from analysis boron container in the form of mixture boric acid feed liquid, solid-liquid point
From 4min, wet product quality is compared.Test data is following table 2.
Table 2 mentions the natural evaporation experimental data table under lithium borate waste solution difference pH
For the stereoscan photograph of gained boric acid crystallization as shown in fig. 7, in Fig. 7, a figure is flaky crystal；B figure is needle-shaped knot
Crystalline substance, c figure are column crystallization.
By embodiment as can be seen that the present invention can be promoted by the liquid level depth in control analysis boron salt field and the pH of waste liquid
Grown up into boric acid with the formation of monocrystalline, the average particle size of product reaches 1.0mm or more, and the entrainment for reducing impure mother liquor is advantageous
In the raising of product quality；Otherwise boric acid will be formed in the form of needle-shaped or sheet, the average particle size of product in 0.5mm hereinafter,
A large amount of flaky crystal, fine needle crystal are in crystalline substance and intergranular carries a large amount of impure mother liquors secretly, to affect the yield of boron, increase
Product operation cost, the improvement for being more difficult to product quality are added.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of from proposing the method for preparing boric acid in lithium borate waste solution, which comprises the following steps:
(1) pH value for mentioning lithium borate waste solution is adjusted to 3.5~4.5, obtains pretreatment and mentions lithium borate waste solution；
(2) pretreatment that the step (1) obtains is mentioned into lithium borate waste solution and is discharged into analysis boron salt field, carried out natural evaporation crystallization, obtain
To high quality boric acid crystal and mother liquid of boric acid；
(3) the boric acid crystal and part mother liquid of boric acid obtained the step (2) is in the form of mixture boric acid feed liquid from analysis boron
After salt pan is produced, dense thickening, the supernatant of dense thickening feed liquid deposited the boric acid magma for forming lower layer and upper layer are carried out；
(4) the boric acid magma in the step (3) is separated by solid-liquid separation, obtains boric acid and boron-bearing liquid.
2. according to claim 1 from proposing the method for preparing boric acid in lithium borate waste solution, which is characterized in that the step
(1) pH value that lithium borate waste solution is mentioned in is 0.1~6.5.
3. according to claim 1 or 2 from proposing the method for preparing boric acid in lithium borate waste solution, which is characterized in that the step
Suddenly the source that lithium borate waste solution is mentioned in (1) includes that salt lake bittern proposes lithium process or oil field water proposes lithium process.
4. according to claim 1 or 2 from proposing the method for preparing boric acid in lithium borate waste solution, which is characterized in that the step
Suddenly adjusting in (1) and mentioning reagent used in lithium borate waste solution pH value includes quick lime, lime stone, magnesia, magnesium sulfate, hydroxide
One of sodium, sodium carbonate, sodium bicarbonate, hydrochloric acid or sulfuric acid are a variety of.
5. according to claim 1 from proposing the method for preparing boric acid in lithium borate waste solution, which is characterized in that the step
(2) analysis boron salt field is piled up by clay in, and bottom is laid with uvioresistant barrier plastic membrane material.
6. according to claim 1 or 5 from proposing the method for preparing boric acid in lithium borate waste solution, which is characterized in that the step
Suddenly analysis boron salt Tanaka level is 1~3m in (2).
7. according to claim 1 from proposing the method for preparing boric acid in lithium borate waste solution, which is characterized in that the step
(3) solid content of dense thickening feed liquid is 30~60% in.
8. according to claim 1 from proposing the method for preparing boric acid in lithium borate waste solution, which is characterized in that further include, it will
The supernatant that the step (3) obtains is discharged into analysis boron salt field and is evaporated crystallization.
9. according to claim 1 from proposing the method for preparing boric acid in lithium borate waste solution, which is characterized in that further include, it will
The boron-bearing liquid that the step (4) obtains is discharged into analysis boron salt field and is evaporated crystallization.
10. according to claim 1 from proposing the method for preparing boric acid in lithium borate waste solution, which is characterized in that the step
(4) mass percentage of boric acid is 87~98% in the boric acid obtained.
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