CN115672256A - Micron-sized lithium ion sieve micro-H 2 TiO 3 Preparation method of the ion sieve and salt lake lithium extraction system applying the ion sieve - Google Patents
Micron-sized lithium ion sieve micro-H 2 TiO 3 Preparation method of the ion sieve and salt lake lithium extraction system applying the ion sieve Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 146
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 145
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
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- 238000003860 storage Methods 0.000 claims description 33
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- 239000000843 powder Substances 0.000 abstract description 41
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 106
- 239000003463 adsorbent Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 8
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- 238000012512 characterization method Methods 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
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- 238000005469 granulation Methods 0.000 description 5
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 239000011858 nanopowder Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a micron-sized lithium ion sieve micro-H 2 TiO 3 The preparation method comprises the steps of firstly, preparing nano-scale lithium ion sieve precursor nano-Li 2 TiO 3 micro-Li converted into micron-sized lithium ion sieve precursor 2 TiO 3 Then the micro-Li precursor of the micron-sized lithium ion sieve is subjected to 2 TiO 3 Acidizing with hydrochloric acid to obtain the micron-sized lithium ion sieve micro-H 2 TiO 3 . The invention also provides micro-H applying the micron-sized lithium ion sieve 2 TiO 3 The salt lake lithium extraction system is matched with the suction effect of the hollow fiber ultrafiltration membrane, dilute hydrochloric acid is used as eluent, and the salt lake lithium extraction is realized through the adsorption-elution operation, so that the effective lithium ion adsorption is realized, and the lithium ion sieve molecular powder is effectively lost in the adsorption process.
Description
Technical Field
The invention relates to the technical field of lithium extraction in salt lake, in particular to a micron-sized lithium ion sieve micro-H capable of intercepting lithium ions in water 2 TiO 3 Also relates to the micron-sized lithium ion sieve micro-H obtained by applying the preparation method 2 TiO 3 Salt lake lithium extraction system.
Background
Lithium and its compounds are widely used in the fields of medicine, ceramics, glass, chemical industry, electronics, etc., and are receiving much attention. With the continuous expansion of the demand for lithium and its compounds, the shortage of lithium resources on land is increasing, and people look to salt lakes with abundant lithium resources. Because the lithium concentration in the salt lake is low, the lithium ion sieve adsorbing material becomes the most promising material for extracting lithium from the salt lake and the most practical material, and becomes the hot point of research of scientists. The method for adsorbing lithium in the salt lake by using the lithium ion sieve with high adsorption capacity and high selectivity is a simple, easy, economical and green method for solving the problem of lithium resource shortage.
Existing lithium ion sieve H commonly used for extracting lithium from salt lake 2 TiO 3 The synthesized powder is nano-grade powder with the average particle size of 30-100nm, and the powder is precipitated and hardened in water or lost when being directly added into water for adsorption, so that the powder is generally required to be molded. The general powder forming technology is to use a binder to bond and form the nanometer lithium ion sieve into particles, and the particles are filled in an adsorption column for adsorption. However, the adsorption capacity of the formed particle lithium ion sieve is reduced by about 50% compared with the powder lithium ion sieve because a plurality of nano powders are wrapped or sealed by the binder, the reduction of the adsorption capacity directly reduces the effective utilization rate of the lithium ion sieve, the floor area of an adsorption system is increased, and the engineering cost is increased. If the forming treatment is not adopted, the particle size of the lithium ion sieve powder is 30-100nm, the ultrafiltration membrane cannot retain the lithium ion, and the nanoscale powder passes through membrane pores of the ultrafiltration membrane and is largely lost, so that the process of 'powder adsorption and ultrafiltration membrane separation' cannot be directly adopted for extracting lithium from the salt lake.
For example, chinese patent application CN 110975795A discloses a synthesis method of a lithium extraction adsorbent, which first prepares a lithium ion sieve adsorbent precursor Li through calcination 2 TiO 3 Then the precursor Li 2 TiO 3 Acid elution of lithium to obtain metatitanic acid type lithium ion sieve adsorbent H 2 TiO 3 . According to the description, the metatitanic acid type lithium ion sieve adsorbent H is used in a lithium solution 2 TiO 3 The adsorption capacity is 33-39mg/g. Obviously, such a powdered material presents the technical drawbacks described previously.
The Chinese patent application CN 112871127A discloses a preparation method of high-porosity lithium ion sieve particles, which comprises the steps of grinding a lithium ion sieve, mixing the ground lithium ion sieve with a pore-forming agent, a filler and an aqueous resin emulsion, extruding and molding, heating to complete the drying and curing process, and finally performing acid leaching and water washing to obtain the lithium ion sieve particles. In the patent, an aqueous resin emulsion is used as a binder, so that an organic solvent can be avoided, but the adsorption capacity and the adsorption rate of the formed adsorbent are lower than those of powder, so that the problem of reduced adsorption performance of the formed particles cannot be solved, and the adsorption amount is 12.6-18.1mg/g.
The Chinese patent application CN112871126A discloses a preparation method of high-adsorption-capacity lithium ion sieve particles, which comprises the steps of sanding lithium ion sieve powder, mixing the sanded lithium ion sieve powder with an inorganic binder, spray-drying, mixing the prepared micron-sized particles with a template pore-forming agent, mixing the obtained micron-sized particles with an aqueous resin emulsion in granulation equipment, granulating, heating to complete drying and curing processes, and finally performing acid leaching and water washing. The granulation process of this patent is relatively complex and has an adsorption capacity of about 22.2 to 25.1mg/g.
Chinese patent application CN113996274A discloses a porous composite lithium adsorbent and a preparation method thereof, wherein inorganic lithium adsorbent powder, a polymer framework material and an auxiliary agent are uniformly mixed with a volatile organic solvent and a water-soluble organic solvent to obtain a composite lithium adsorbent precursor mixture; and (3) granulating the precursor mixture, and placing the granulated precursor mixture in an atmosphere environment with certain flow rate, humidity and temperature to obtain the porous composite lithium adsorbent. The granulation process of the patent is relatively complex, the phenomenon of powder falling easily occurs to the granules after granulation, the problem of the reduction of the adsorption performance of the granules after granulation can not be solved, and the adsorption capacity is about 2-21 mg/g.
Chinese patent application CN 109266851A discloses a method for extracting lithium by using a magnetic microporous lithium adsorbent, which comprises immersing the magnetic microporous lithium adsorbent in a lithium-containing solution to make at least part of lithium ions adsorbed by the magnetic microporous lithium adsorbent; separating the magnetic microporous lithium adsorbent from the mixed system, and desorbing lithium ions in the magnetic microporous lithium adsorbent by using water. The technology does not need to granulate the lithium ion sieve, can furthest keep the adsorption performance of the lithium ion sieve powder, but can separate the magnetic substance from the lithium ion sieve powder in the continuous use process due to the fact that the binding force between the magnetic substance and the lithium ion sieve powder is not strong enough, so that the lithium ion sieve powder is lost and loses magnetism, and the lithium ion sieve powder cannot be continuously used.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a lithium ion sieve which can be directly added into a water body for adsorption without large loss, can not cause blockage or sealing of other parts in a lithium extraction system in a salt lake and can be effectively recycled.
The idea of the invention is to firstly prepare nano-scale lithium ion sieve precursor nano-Li 2 TiO 3 micro-Li converted into micron-sized lithium ion sieve precursor 2 TiO 3 Then the micro-Li precursor of the micron-sized lithium ion sieve is subjected to 2 TiO 3 Acidizing with hydrochloric acid to obtain micro-H of the micron-sized lithium ion sieve 2 TiO 3 . Then a set of micro-H applied lithium ion sieve is designed 2 TiO 3 The salt lake lithium extraction system is matched with an ultrafiltration membrane capable of reciprocating to carry out solid-liquid separation, verifies the lithium ion sieve and the effective utilization rate and the adsorption capacity, verifies the performances of the lithium ion sieve powder such as stability of the adsorption capacity, change of the adsorption rate, powder utilization rate and the like, and confirms whether powder loss can be avoided.
In order to achieve the above objects, the present invention provides a micro-H lithium ion sieve having micro-sized particles 2 TiO 3 The method for preparing (1), the method comprising the steps of:
(1) Preparation of nano-scale lithium ion sieve precursor nano-Li 2 TiO 3
Taking anatase type titanium dioxide and lithium carbonate powder according to a molar ratio of 1 2 TiO 3 ；
(2) Preparation of micron-sized lithium ion sieve precursor nano-Li 2 TiO 3
Taking polyvinyl chloride, polyvinyl butyral and polyvinylidene fluoride as composite bondingThe mass of the composite binder is the composite binder and a nano-scale lithium ion sieve precursor Li 2 TiO 3 5-15% of the total mass, taking dimethyl acetamide as the organic solvent of the composite binder, the mass of the dimethyl acetamide and the precursor Li of the nano-scale lithium ion sieve 2 TiO 3 1.5-2;
polyvinyl chloride, polyvinyl butyral, polyvinylidene fluoride and nano-scale lithium ion sieve precursor Li 2 TiO 3 Fully stirring the mixture and dimethylacetamide at 50-80 ℃ to obtain mixed slurry, then adding deionized water with the mass 4-8 times that of the dimethylacetamide into the mixed slurry under high-speed stirring, fully stirring, and carrying out suction filtration on the slurry to obtain a filter cake which is a micron-sized lithium ion sieve precursor micro-Li 2 TiO 3 ；
(3) Preparation of micron-sized lithium ion sieve precursor nano-H 2 TiO 3
Subjecting the micron-sized lithium ion sieve precursor micro-Li obtained in the step (2) 2 TiO 3 Placing the mixture in 0.1 to 0.4mol/L hydrochloric acid to lead micro-Li 2 TiO 3 The molar ratio of the slurry to HCl is 1-3, the slurry is fully stirred and then is filtered, and the obtained filter cake is a micron-sized lithium ion sieve micro-H 2 TiO 3 。
The invention firstly prepares nano-grade lithium ion sieve precursor nano-Li 2 TiO 3 micro-Li converted into micron-sized lithium ion sieve precursor 2 TiO 3 Then to micro-Li of the micron-sized lithium ion sieve precursor 2 TiO 3 Acidizing with hydrochloric acid to obtain the micron-sized lithium ion sieve micro-H 2 TiO 3 The process has two major effects: first, nano-Li 2 TiO 3 If the powder is directly acidified, the average particle size of the powder is small, so that the nano powder cannot be intercepted by the ultra-filtration membrane, and the powder loss is serious. The invention firstly uses nano-Li 2 TiO 3 Powder is converted into micro-Li 2 TiO 3 Then acidification is carried out, the average particle size is larger, so that the combination of the lithium ion sieve and the ultrafiltration membrane in water is realized, the ultramicro filtration membrane can be used for intercepting powder, and the problem of application of the ultramicro filtration membrane is solvedThe powder loss in the process; second, nano-Li 2 TiO 3 If the powder is directly granulated and formed into particles with the diameter of 1-5mm, and then is acidified, because a large amount of nano powder is wrapped or sealed by the binder, the part of nano powder cannot be acidified, and the utilization rate of the lithium ion sieve particles obtained by the structure is very low. The invention relates to nano-Li 2 TiO 3 The powder is firstly converted into micro-Li 2 TiO 3 The powder is acidified, and the average grain diameter of the obtained powder is 0.5-50 mu m, thereby avoiding the defect that a large amount of nano powder is included or closed and cannot be acidified.
According to a preferred embodiment, the mechanical stirring time of step (1) is 1-2h until the materials are well mixed.
In the invention, the proportion of the polyvinyl chloride, the polyvinyl butyral and the polyvinylidene fluoride in the step (2) is 1:1 to 2:1 to 3.
Preferably, in the step (2), polyvinyl chloride, polyvinyl butyral, polyvinylidene fluoride and nano-scale lithium ion sieve precursor Li are added 2 TiO 3 And dimethyl acetamide are stirred for 5 to 10 hours at the temperature of between 50 and 80 ℃ to obtain mixed slurry. Deionized water was added to the mixed slurry at a flow rate of 0.1-1L/min.
Preferably, the stirring time of step (3) is 10-20h.
The invention also provides the micron-sized lithium ion sieve micro-H prepared by the preparation method 2 TiO 3 The application in extracting lithium from salt lake.
Based on the technical scheme, the invention provides a micro-H applied micron-sized lithium ion sieve 2 TiO 3 The lithium extraction system for the salt lake comprises a pool body (1), a hydrochloric acid storage tank (3), a salt lake brine storage tank (9), a hollow fiber ultrafiltration membrane (11) and a driving motor (12), wherein the driving motor (12) is connected with the hollow fiber ultrafiltration membrane (11) and drives the hollow fiber ultrafiltration membrane (11) to reciprocate, an aeration device (2) is arranged at the bottom of the pool body (1), the hydrochloric acid storage tank (3) and the salt lake brine storage tank (9) are respectively connected with the bottom of the pool body (1) through pipelines, and the lithium extraction system is characterized in that the micron-sized lithium extraction system is arranged in the pool body (1) and is obtained by the preparation method according to any one of claims 1-6Lithium ion grade sieve micro-H 2 TiO 3 Micron-sized lithium ion sieve micro-H 2 TiO 3 The concentration of the eluent is 100g/L-200g/L, the grain diameter is 0.5-50 μm, and a hydrochloric acid storage tank (3) is filled with 0.1-0.4mol/L dilute hydrochloric acid as eluent.
The operation of the salt lake lithium extraction system is as follows:
(1) Adsorption stage
And (3) starting adsorption: lithium-containing salt lake brine enters into micro-H with a micron-sized lithium ion sieve from a salt lake brine storage tank (9) 2 TiO 3 The hydraulic retention time in the pool body (1) is 1-5BV/h, the aeration rate is 100-200L/min by opening the aeration device (2), when the water level of the pool body (1) reaches 80-90% of the height of the pool body, the driving motor (12) is started to make the hollow fiber ultrafiltration membrane (11) reciprocate, the reciprocating frequency is 0.5-5Hz, the hollow fiber ultrafiltration membrane (11) is sucked under negative pressure by the ultrafiltration membrane negative pressure suction device to obtain ultrafiltration membrane produced water, and at the moment, the inflow of the salt lake brine storage tank (9) to the pool body (1) is equal to the produced water flow of the ultrafiltration membrane;
stopping adsorption: monitoring the concentration of lithium ions in the water produced by the ultrafiltration membrane, and considering the micro-H of the micron-sized lithium ion sieve when the concentration of the lithium ions in the produced water is 50-80% of the concentration of the lithium ions in the water inlet pipe of the effluent of the salt lake brine storage tank (9) 2 TiO 3 When the adsorption reaches saturation, stopping water inflow of the salt lake brine storage tank (9) to the tank body (1), stopping the ultrafiltration membrane negative pressure suction device to enable the hollow fiber ultrafiltration membrane (11) to stop producing water, stopping aeration, stopping the reciprocating motion of the hollow fiber ultrafiltration membrane (11), opening the ultrafiltration membrane negative pressure suction device to suck the brine in the tank body (1) through the hollow fiber ultrafiltration membrane (11) after natural sedimentation is carried out for 5-10min, and stopping the ultrafiltration membrane negative pressure suction device when the water level of the tank body (1) is reduced to 20% -30% of the height of the tank;
(2) Elution phase
Introducing a dilute hydrochloric acid tank of a hydrochloric acid storage tank (3) into a tank body (1), starting an ultrafiltration membrane negative pressure suction device, keeping the hydraulic retention time at 1-3BV/h, monitoring the pH value of the ultrafiltration membrane produced water, stopping introducing eluent when the pH value is the same as that of dilute hydrochloric acid in the hydrochloric acid storage tank (3), starting the ultrafiltration membrane negative pressure suction device to enable a hollow fiber ultrafiltration membrane (11) to start negative pressure suction, stopping the negative pressure suction device when the water level of the tank body (1) is reduced to 20% -30% of the height of the tank, ending an elution stage at this moment, and entering an adsorption stage again.
The invention relates to nano-scale nano-Li-precursor of lithium ion sieve 2 TiO 3 Starting to obtain the micron-sized lithium ion sieve micro-H 2 TiO 3 Obtaining micro-scale micro-H 2 TiO 3 Has a specific surface area and a pore volume which are obviously smaller than those of nano-Li 2 TiO 3 . The salt lake lithium extraction system designed based on the ionic sieve material verifies the effective utilization rate and the adsorption capacity of the lithium ionic sieve, confirms that the lithium ionic sieve powder has the characteristics of stable adsorption capacity and high powder utilization rate, and can effectively avoid powder loss.
Drawings
FIG. 1 is the nano-sized lithium ion sieve precursor nano-Li of example 1 2 TiO 3 And micron-sized lithium ion sieve micro-H 2 TiO 3 SEM photograph of (a);
FIG. 2 is the nano-sized lithium ion sieve precursor nano-Li of example 2 2 TiO 3 And micron-sized lithium ion sieve micro-H 2 TiO 3 SEM photograph of (a);
FIG. 3 is a schematic structural diagram of a lithium extraction system of the salt lake of example 1.
Detailed Description
The following examples serve to illustrate the technical solution of the present invention without limiting it.
In the present invention, "%" used for describing the concentration is mass percent, ": "is a mass ratio.
Example 1
Preparation of nano-scale lithium ion sieve precursor nano-Li 2 TiO 3 ：
Taking the mass ratio of anatase titanium dioxide to lithium carbonate powder as 1.1, placing the anatase titanium dioxide to lithium carbonate powder in a stirrer, mechanically stirring and mixing for 1h, then placing the uniformly mixed powder in a muffle furnace, and roasting for 3h at 700 ℃ to obtain a nano-scale lithium ion sieve precursor nano-Li 2 TiO 3 。
Preparation of micron-sized lithium ion sieve precursor micro-Li 2 TiO 3 ：
Weighing polyvinyl chloride (PVC), polyvinyl butyral (PVB) and polyvinylidene fluoride (PVDF) with equal mass as composite binders, and controlling the composite binders and a nano-scale lithium ion sieve precursor Li 2 TiO 3 The mass ratio of (a) to (b) is 5. Measuring dimethylacetamide (DMAc) as an organic solvent of the composite binder, and controlling the quality of the DMAc and the Li precursor of the nanoscale lithium ion sieve 2 TiO 3 The mass ratio of (1) to (1) is 1.5. Polyvinyl chloride (PVC), polyvinyl butyral (PVB), polyvinylidene fluoride (PVDF) and nano-scale lithium ion sieve precursor Li 2 TiO 3 And dimethylacetamide (DMAc) at 50 ℃ for 5h until mixed well to give a mixed slurry. Measuring deionized water with the mass 4 times that of DMAc, adding the deionized water into the mixed slurry under high-speed stirring, controlling the flow rate of the deionized water to ensure that all the deionized water is added into the mixed slurry within 1 hour, and then continuously stirring for 1 hour. After stirring is stopped, the mixed material is filtered, and the obtained filter cake is micron-sized lithium ion sieve precursor micro-Li 2 TiO 3 。
Preparation of micron-sized lithium ion sieve micro-H 2 TiO 3 : measuring 0.1mol/L hydrochloric acid, micro-Li 2 TiO 3 Mass ratio to HCl 1 2 TiO 3 Placing in hydrochloric acid, stirring for 10H to ensure uniform mixing of the materials, carrying out suction filtration on the mixed materials, and obtaining a filter cake which is a micron-sized lithium ion sieve micro-H 2 TiO 3 。
The nanometer lithium ion sieve precursor nano-Li is subjected to surface area analysis by a BET (BET surface area analysis) full-automatic surface area and porosity analysis instrument (American Micromeritics ASAP2020HD 88) 2 TiO 3 And micron-sized lithium ion sieve micro-H 2 TiO 3 The characterization was performed to obtain the data in Table 1, which indicates that micro-H 2 TiO 3 Has a specific surface area and a pore volume which are obviously smaller than that of nano-Li 2 TiO 3 。
TABLE 1 nano-Li 2 TiO 3 And micro-H 2 TiO 3 BET characterization of
An LS-609 type laser particle size analyzer (Euromecon instruments) is adopted to analyze nano-grade lithium ion sieve precursor nano-Li 2 TiO 3 And micron-sized lithium ion sieve micro-H 2 TiO 3 The characterization is carried out to obtain the data in Table 2, and the nano-scale lithium ion sieve precursor nano-Li can be known 2 TiO 3 Has a particle size of about 10-60nm, and a micron-sized lithium ion sieve micro-H 2 TiO 3 Has a particle size of about 5 to 40 μm.
TABLE 2 nano-Li 2 TiO 3 And micro-H 2 TiO 3 BET characterization of
Nano-scale lithium ion sieve precursor nano-Li 2 TiO 3 And micron-sized lithium ion sieve micro-H 2 TiO 3 The SEM photograph of (A) is shown in FIG. 1.
Verification of the resulting nano-H 2 TiO 3 (from nano-Li) 2 TiO 3 Obtained after acidification) and micro-H 2 TiO 3 Lithium ion adsorption capacity of (2):
1g of nano-H in powder form 2 TiO 3 And micro-H 2 TiO 3 1L of an aqueous solution of lithium hydroxide was put into the flask, the concentration of lithium ions in the solution was 300mg/L, the mixture was stirred for 3 hours, a water sample was taken to analyze the concentration of lithium ions, and the adsorption capacities of the two materials were calculated from the difference in the concentration of lithium ions, thereby obtaining the data shown in Table 3. It can be seen from the calculation that micro-H of the present embodiment 2 TiO 3 Has an adsorption capacity of nano-H 2 TiO 3 93.2% of the adsorption capacity of (1).
TABLE 3 nano-Li 2 TiO 3 And micro-H 2 TiO 3 BET characterization of
micro-H 2 TiO 3 The brine lithium extraction experiment:
the system as shown in figure 3 is arranged, a uniformly distributed micropore aeration net 2 is arranged at the bottom of a stainless steel tank body 1, and the tank body is internally provided with good uniform aeration. The device is characterized in that a hydrochloric acid storage tank 3 and a salt lake brine storage tank 9 are respectively connected through a hydrochloric acid pipeline and a brine pipeline, a hydrochloric acid inlet pipe pH online detector 4 and a hydrochloric acid inlet pipe suction pump 5 are arranged on the hydrochloric acid pipeline, a salt lake brine inlet pipe suction pump 7 and a salt lake brine inlet pipe lithium ion concentration online monitor 8 are arranged on the brine pipeline, and the two pipelines are finally connected to a pool body liquid inlet 6 located at the bottom of a pool. A U-shaped hollow fiber ultrafiltration membrane 11 is arranged in a stainless steel tank body 1, the membrane is arranged on an ultrafiltration membrane water production plate frame 17, and the reciprocating swing of the ultrafiltration membrane in the tank body is realized through a swing power support 16 and a swing ultrafiltration membrane power motor device 12 connected with the support. An ultrafiltration membrane water production pipeline 15 is provided with a water production pipe lithium ion concentration online monitor 13 and a water production pipe pH online detector 14.
micro-H of micron-sized lithium ion sieve is loaded in the tank body 2 TiO 3 The loading capacity is 100g/L based on the total solvent of the tank body, and the liquid level height in the tank body is usually maintained at 80-90% of the height of the tank body in the operation stage.
The hydrochloric acid storage tank 3 is filled with 0.1mol/L dilute hydrochloric acid.
The salt lake brine storage tank 9 is loaded with salt lake brine to be treated.
During operation, salt lake brine in the salt lake brine storage tank 9 enters the tank body, the hydraulic retention time is 2BV/h, the aeration device is opened to enable the ratio (gas-water ratio) of aeration rate to membrane fiber water yield to be 30.
When the concentration of the lithium ions in the produced water is monitored by the online lithium ion concentration monitor 13, the concentration of the lithium ions in the produced water is the concentration of the lithium ions in the water inlet pipe of the salt lake brine storage tank 9At 50% of the degree, the micron-sized lithium ion sieve is considered to be micro-H 2 TiO 3 When the adsorption reaches saturation, stopping water inflow of the salt lake brine storage tank (9) to the tank body (1), stopping the ultrafiltration membrane negative pressure suction device to enable the hollow fiber ultrafiltration membrane (11) to stop producing water, stopping aeration, stopping the reciprocating motion of the hollow fiber ultrafiltration membrane (11), opening the ultrafiltration membrane negative pressure suction device to suck the brine in the tank body (1) through the hollow fiber ultrafiltration membrane (11) after natural sedimentation is carried out for 5-10min, and stopping the ultrafiltration membrane negative pressure suction device when the water level of the tank body (1) is reduced to 20% -30% of the height of the tank;
introducing a dilute hydrochloric acid tank of a hydrochloric acid storage tank (3) into a tank body (1), starting an ultrafiltration membrane negative pressure suction device, keeping the hydraulic retention time at 1BV/h, monitoring the pH value of the ultrafiltration membrane produced water, stopping introducing eluent when the pH value is the same as the dilute hydrochloric acid pH value of the hydrochloric acid storage tank (3), starting the ultrafiltration membrane negative pressure suction device to start negative pressure suction on a hollow fiber ultrafiltration membrane (11), and stopping the negative pressure suction device when the water level of the tank body (1) is reduced to 20% -30% of the height of the tank.
The experiment of detecting brine of a salt lake in Tibet is to detect the inlet water concentration and the produced water concentration of each component in the brine, as shown in Table 4.
TABLE 4 analysis of the concentrations of the components in the process of extracting lithium
The experimental result shows that the system can realize the selective extraction of lithium ions in the brine, and the extraction rate of lithium is as high as 96.7%. In addition, the water produced after the membrane filaments are filtered is analyzed for titanium element, and the fact that the titanium element does not exist in the water is found, so that the fact that the dissolved titanium element does not exist in the water and powder particles which can penetrate through the membrane filaments do not exist, namely powder loss does not exist.
Example 2
Preparation of nano-scale lithium ion sieve precursor nano-Li 2 TiO 3 ：
Taking the mass ratio of anatase titanium dioxide to lithium carbonate powder as 1.5, placing the anatase titanium dioxide and lithium carbonate powder in a stirrer, mechanically stirring and mixing for 3 hours, and then placing the uniformly mixed powder in a stirrerRoasting in a muffle furnace at 850 ℃ for 4h to obtain nano-scale lithium ion sieve precursor nano-Li 2 TiO 3 。
Preparation of micron-sized lithium ion sieve precursor micro-Li 2 TiO 3 ：
Weighing polyvinyl chloride (PVC), polyvinyl butyral (PVB) and polyvinylidene fluoride (PVDF) with equal mass as composite binders, and controlling the composite binders and a nano-scale lithium ion sieve precursor Li 2 TiO 3 The mass ratio of (1) is 15. Measuring dimethylacetamide (DMAc) as an organic solvent of the composite binder, and controlling the quality of the DMAc and the Li precursor of the nanoscale lithium ion sieve 2 TiO 3 The mass ratio of (1) is 2. Polyvinyl chloride (PVC), polyvinyl butyral (PVB), polyvinylidene fluoride (PVDF) and nano-scale lithium ion sieve precursor Li 2 TiO 3 And dimethylacetamide (DMAc) at 60 ℃ until mixed well to give a mixed slurry. Measuring deionized water with the mass 5 times that of DMAc, adding the deionized water into the mixed slurry under high-speed stirring, controlling the flow rate of the deionized water to ensure that all the deionized water is added into the mixed slurry within 1 hour, and then continuously stirring for 1 hour. After stirring is stopped, the mixed material is filtered, and the obtained filter cake is micron-sized lithium ion sieve precursor micro-Li 2 TiO 3 。
Preparation of micron-sized lithium ion sieve micro-H 2 TiO 3 : measuring 0.2mol/L hydrochloric acid, micro-Li 2 TiO 3 The mass ratio of the micro-sized lithium ion sieve precursor to HCl is 1 2 TiO 3 Placing in hydrochloric acid, stirring for 10H to ensure uniform mixing of the materials, carrying out suction filtration on the mixed materials, and obtaining a filter cake which is a micron-sized lithium ion sieve micro-H 2 TiO 3 。
The specific surface area and pore volume of the obtained lithium ion sieve were measured.
TABLE 5 nano-Li 2 TiO 3 And micro-H 2 TiO 3 BET characterization of
The particle size of the resulting lithium ion sieve was measured.
TABLE 6 nano-Li 2 TiO 3 And micro-H 2 TiO 3 BET characterization of
Nano-scale lithium ion sieve precursor nano-Li 2 TiO 3 And micron-sized lithium ion sieve micro-H 2 TiO 3 The SEM photograph of (1) is shown in FIG. 2.
Similarly, verification was performed using the system as shown in example 1 and FIG. 3, except that the inside of the cell body was micro-H-lithium ion sieve of micron size 2 TiO 3 The loading capacity is 200g/L based on the total solvent of the pool body. The hydrochloric acid storage tank 3 is filled with 0.2mol/L dilute hydrochloric acid. When the concentration of lithium ions in produced water is 80% of that of lithium ions in a water inlet pipe of a salt lake brine storage tank 9, the micron-sized lithium ion sieve micro-H is considered 2 TiO 3 The adsorption reached saturation.
The experiment of detecting brine of a salt lake in Tibet is to detect the influent water concentration and the produced water concentration of each component in the brine, as shown in Table 7.
TABLE 7 analysis of the concentrations of the components in the lithium extraction process
The experimental result shows that the system can realize the selective extraction of lithium ions in the brine, and the extraction rate of lithium is up to 96.2%. In addition, the water produced after the membrane filaments are filtered is analyzed for titanium element, and the fact that the titanium element does not exist in the water is found, so that the fact that the titanium element in a dissolved state does not exist in the water and powder particles capable of penetrating through the membrane filaments do not exist in the water is proved, namely, no powder is lost.
Claims (9)
1. Micron-sized lithium ion sieve micro-H 2 TiO 3 The method comprises the following steps:
(1) Preparation of nano-grade lithium ion sieve precursor nano-Li 2 TiO 3
According to the mol ratio of 1 2 TiO 3 ；
(2) Nano-Li for preparing micron-sized lithium ion sieve precursor 2 TiO 3
Taking polyvinyl chloride, polyvinyl butyral and polyvinylidene fluoride as a composite binder, wherein the mass of the composite binder is that the composite binder and a nanometer lithium ion sieve precursor Li 2 TiO 3 5-15 percent of the total mass, taking dimethyl acetamide as the organic solvent of the composite binder, the mass of the dimethyl acetamide and the precursor Li of the nano-scale lithium ion sieve 2 TiO 3 The mass ratio of (A) to (B) is 1.5-2;
polyvinyl chloride, polyvinyl butyral, polyvinylidene fluoride and nano-scale lithium ion sieve precursor Li 2 TiO 3 Fully stirring the mixture and dimethylacetamide at 50-80 ℃ to obtain mixed slurry, then adding deionized water with the mass 4-8 times that of the dimethylacetamide into the mixed slurry under high-speed stirring, fully stirring, and carrying out suction filtration on the slurry to obtain a filter cake which is a micron-sized lithium ion sieve precursor micro-Li 2 TiO 3 ；
(3) Preparation of micron-sized lithium ion sieve precursor nano-H 2 TiO 3
Subjecting the micron-sized lithium ion sieve precursor micro-Li obtained in the step (2) 2 TiO 3 Placing the mixture in 0.1 to 0.4mol/L hydrochloric acid to lead micro-Li 2 TiO 3 The molar ratio of the slurry to HCl is 1 2 TiO 3 。
2. The process according to claim 1, wherein the mechanical stirring time in step (1) is 1 to 2 hours.
3. The method according to claim 1, wherein in the step (2), the composite binder is a mixture of 1:1 to 2: 1-3 of polyvinyl chloride, polyvinyl butyral and polyvinylidene fluoride.
4. The method according to claim 1, wherein in the step (2), polyvinyl chloride, polyvinyl butyral, polyvinylidene fluoride, and nano-sized lithium ion sieve precursor Li are mixed 2 TiO 3 And dimethyl acetamide are stirred for 5 to 10 hours at the temperature of between 50 and 80 ℃ to obtain mixed slurry.
5. The method according to claim 1, wherein in the step (2), the deionized water is added to the mixed slurry at a constant flow rate for 1 to 3 hours at a constant speed.
6. The process according to claim 1, wherein the stirring time in the step (3) is 10 to 20 hours.
7. The micron-sized lithium ion sieve micro-H obtained by the preparation method of claims 1 to 6 2 TiO 3 The application in extracting lithium from salt lake.
8. micro-H applying micron-sized lithium ion sieve 2 TiO 3 The lithium extraction system for the salt lake comprises a pool body (1), a hydrochloric acid storage tank (3), a salt lake brine storage tank (9), a hollow fiber ultrafiltration membrane (11) and a drive motor (12), wherein the drive motor (12) is connected with the hollow fiber ultrafiltration membrane (11) and drives the hollow fiber ultrafiltration membrane (11) to reciprocate, an aeration device (2) is arranged at the bottom of the pool body (1), the hydrochloric acid storage tank (3) and the salt lake brine storage tank (9) are respectively connected with the bottom of the pool body (1) through pipelines, and the lithium micron-sized ion sieve micro-H system is characterized in that the lithium micron-sized ion sieve micro-H-sized ion sieve obtained by the preparation method according to any one of claims 1 to 6 is arranged in the pool body (1) 2 TiO 3 Micron-sized lithium ion sieve micro-H 2 TiO 3 The concentration of the filter is 100g/L-200g/L calculated by the total volume of the tank body, and the particle diameter is 0.5-50Mu m, and a hydrochloric acid storage tank (3) is filled with 0.1-0.4mol/L dilute hydrochloric acid as eluent.
9. The salt lake lithium extraction system of claim 8, wherein the system operates as follows:
(1) Adsorption phase
And (3) starting adsorption: lithium-containing salt lake brine enters into micro-H filled with micron-sized lithium ion sieve from a salt lake brine storage tank (9) 2 TiO 3 When the water level of the pool body (1) reaches 80% -90% of the pool height of the pool body, starting a driving motor (12) to enable a hollow fiber ultrafiltration membrane (11) to reciprocate, wherein the reciprocating frequency is 0.5-5Hz, and performing negative pressure suction on the hollow fiber ultrafiltration membrane (11) through an ultrafiltration membrane negative pressure suction device to obtain ultrafiltration membrane produced water, wherein the inflow flow of salt lake brine from a storage tank (9) to the pool body (1) is equal to the water production flow of the ultrafiltration membrane;
stopping adsorption: monitoring the concentration of lithium ions in the water produced by the ultrafiltration membrane, and considering the micro-H of the micron-sized lithium ion sieve when the concentration of the lithium ions in the produced water is 50-80% of the concentration of the lithium ions in the water inlet pipe of the effluent of the salt lake brine storage tank (9) 2 TiO 3 When the adsorption reaches saturation, stopping water inflow of the salt lake brine storage tank (9) to the tank body (1), stopping the ultrafiltration membrane negative pressure suction device to enable the hollow fiber ultrafiltration membrane (11) to stop producing water, stopping aeration, stopping the reciprocating motion of the hollow fiber ultrafiltration membrane (11), opening the ultrafiltration membrane negative pressure suction device to suck the brine in the tank body (1) through the hollow fiber ultrafiltration membrane (11) after natural sedimentation is carried out for 5-10min, and stopping the ultrafiltration membrane negative pressure suction device when the water level of the tank body (1) is reduced to 20% -30% of the height of the tank;
(2) Elution phase
Introducing a dilute hydrochloric acid tank of a hydrochloric acid storage tank (3) into a tank body (1), starting an ultrafiltration membrane negative pressure suction device, keeping the hydraulic retention time at 1-3BV/h, monitoring the pH value of the ultrafiltration membrane produced water, stopping introducing eluent when the pH value is the same as that of dilute hydrochloric acid in the hydrochloric acid storage tank (3), starting the ultrafiltration membrane negative pressure suction device to enable a hollow fiber ultrafiltration membrane (11) to start negative pressure suction, stopping the negative pressure suction device when the water level of the tank body (1) is reduced to 20% -30% of the height of the tank, ending an elution stage at this moment, and entering an adsorption stage again.
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| US20150258501A1 (en) * | 2014-03-11 | 2015-09-17 | Myongji University Industry And Academia Cooperation Foundation | Composite nanofiber membrane for adsorbing lithium, method of manufacturing the same and apparatus and method for recovering lithium using the same |
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| US20150258501A1 (en) * | 2014-03-11 | 2015-09-17 | Myongji University Industry And Academia Cooperation Foundation | Composite nanofiber membrane for adsorbing lithium, method of manufacturing the same and apparatus and method for recovering lithium using the same |
| CN106622170A (en) * | 2016-12-21 | 2017-05-10 | 江苏大学 | Preparation method and application of lithium-titanium type ion sieve composite membrane |
| CN108636341A (en) * | 2018-04-18 | 2018-10-12 | 南京工业大学 | A kind of forming method carrying lithium adsorbent |
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