CN109225124A - A kind of preparation method of particle lithium adsorbent - Google Patents

A kind of preparation method of particle lithium adsorbent Download PDF

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CN109225124A
CN109225124A CN201811331549.3A CN201811331549A CN109225124A CN 109225124 A CN109225124 A CN 109225124A CN 201811331549 A CN201811331549 A CN 201811331549A CN 109225124 A CN109225124 A CN 109225124A
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lithium
particle
lithium adsorbent
preparation
adsorbent
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孙淑英
刘东帆
于建国
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East China University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination

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  • Organic Chemistry (AREA)
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  • Hydrology & Water Resources (AREA)
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  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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Abstract

The invention discloses a kind of preparation methods of particle lithium adsorbent, the following steps are included: lithium adsorbent or its presoma powder, multiple polymers, pore creating material and organic solvent are mixed under conditions of normal pressure, temperature are 10-190 DEG C, 1-120min is stirred, is obtained a homogeneous mixture；Above-mentioned homogeneous mixture is instilled in solution, or above-mentioned homogeneous mixture extrusion molding is crushed, obtains particle lithium adsorbent by washing.The particle lithium adsorbent of the preparation method preparation of particle lithium adsorbent provided by the invention, granule strength height, good toughness are fitted into non-breakable, dusting in fixed bed or adsorption tower, good hydrophilic property is small with powder adsorbance difference after molding；Simple process, and the solvent used reuse after rectifying, at low cost, environmental pollution is small, is suitable for industrial applications.

Description

A kind of preparation method of particle lithium adsorbent
Technical field
The invention belongs to chemical extraction technical fields, are used for salt lake bittern more particularly to one kind, seawater, GEOTHERMAL WATER, consolidate The preparation method of particle lithium adsorbent in the lithium-containing solutions such as useless leaching liquid.
Background technique
Currently, the problems such as energy shortage, scarcity of resources and environmental pollution, is just threaten the sound development of human civilization.Face To the severe situation of environmental degradation, the exploitation that fossil fuel is greatly decreased is used, and Development of Novel renewable energy has become as people Class common recognition.Lithium battery has the characteristics that high-energy-density, low self-discharge, high circulation service life, memory-less effect, is most to develop at present The high efficient secondary battery of prospect and chemical energy storage power supply with fastest developing speed, the development and application of lithium battery are for improving the utilization of resources Rate solves energy crisis and environment is protected all to have important strategic importance.
Since price is surging, the exploitation of lithium resource at present is that ore and brine technique develop simultaneously, and following industrial focal point will be by Lithium steering brine, which is mentioned, containing lithium ore mentions lithium and retired lithium battery recycling field.The technology for recycling lithium from brine has the precipitation method, film Method, extraction, absorption method etc..The precipitation method are primarily adapted for use in low Mg/Li ratio brine and mention lithium；It is higher that embrane method is mainly applicable in lithium concentration Lithium-containing solution mentions lithium；The application of extraction is limited by equipment corrosion and environmental pollution, fails to be widely applied.
The key of absorption method is the adsorbent of function admirable, and there are many adsorbents to lithium adsorption capacity with higher at present And higher selectivity, common lithium adsorbent have manganese systems lithium ion sieve, titanium based lithium-ion sieve, aluminum salt adsorbent, LiFePO4 Ion sieve etc..But it due to being powder state after the synthesis of these adsorbents, not can be used directly in conventional equipments such as fixed beds It carries out adsorption-desorption and mentions lithium.Therefore, the particle lithium adsorbent with commercial application value, the exploitation to the following lithium resource are developed It is of great significance.
Summary of the invention
The object of the present invention is to provide one kind can directly be industrially applied in salt lake bittern, seawater, GEOTHERMAL WATER, solid waste leaching The lithium-containing solutions such as liquid propose the preparation method of the particle lithium adsorbent of lithium, and the good hydrophilic property of the particle lithium adsorbent of preparation is inhaled with lithium Attached dose of powder is small compared to adsorption capacity variation, easy to operate, at low cost, is easy to industrial applications.
To achieve the goals above, The technical solution adopted by the invention is as follows:
The first aspect of the invention provides a kind of preparation method of particle lithium adsorbent, comprising the following steps:
By lithium adsorbent or its presoma powder, multiple polymers, pore creating material and organic solvent in normal pressure, temperature 10- It is mixed under conditions of 190 DEG C, stirs 1-120min, obtain a homogeneous mixture；The mass ratio of multiple polymers and organic solvent is (0.01-10):1；The mass ratio of pore creating material and organic solvent is (0~0.2): 1；Lithium adsorbent or its presoma powder with it is organic The mass ratio of solvent is (0.1~10): 1；
Above-mentioned homogeneous mixture is instilled in solution, the mass ratio of homogeneous mixture and solution is (0.01~0.3): 1, or Above-mentioned homogeneous mixture extrusion molding is crushed, obtains particle lithium adsorbent by washing.
The lithium adsorbent or its presoma powder be manganese systems lithium ion sieve or its precursor powder, titanium based lithium-ion sieve or At least one of its precursor powder, aluminum salt adsorbent powder, ferric lithium phosphate precursor powder, preferably LiMn2O4 (LiMn2O4Or Li4Mn5O12), aluminum salt adsorbent (LiX2Al (OH)3·nH2O, X represent anion, are Cl-、SO4 2-In one Kind, the value range of n is 0-2), lithium titanate (Li4Ti5O12At least one of).
The multiple polymers are Kynoar, polyethylene, polypropylene, polyvinyl chloride, chliorinated polyvinyl chloride, polyphenyl second Alkene, polyvinylidene chloride, ABS resin, polyamide, polyformaldehyde, polycarbonate, polyether-ketone, polyether sulfone, gathers polyvinylidene fluoride Phenylate, polyurethane, polyvinyl butyral, polyvinylpyrrolidone, polyacrylic acid, polymethyl methacrylate, polyethylene glycol, At least one of polyvinyl alcohol, polyethylene terephthalate.
The pore creating material is sodium chloride, in potassium chloride, sodium sulphate, potassium sulfate, sodium carbonate, potassium carbonate, sodium nitrate, potassium nitrate At least one.
The organic solvent is benzene, toluene, tetrahydrofuran, chloroform, carbon tetrachloride, thionyl chloride, N, N- dimethyl Formamide, DMAC N,N' dimethyl acetamide, perchloroethylene, trichloro ethylene, aromatic hydrocarbons, ethyl acetate, acetone, in N-Methyl pyrrolidone At least one.
Described to instill above-mentioned homogeneous mixture in solution, dropwise addition uses method to be added dropwise for dropper, syringe is added dropwise, pumping Take at least one of dropwise addition.
Described to instill above-mentioned homogeneous mixture in solution, homogeneous mixture is 0.1-1m at a distance from solution.
It is described to instill above-mentioned homogeneous mixture in solution, solution be water, ethyl alcohol, propyl alcohol, ethylene glycol, in acetone at least It is a kind of.
Described to be crushed above-mentioned homogeneous mixture extrusion molding, the temperature of extrusion molding is 0-200 DEG C, extrusion pressure 0- 15MPa。
The washing uses at least one of water, ethyl alcohol, propyl alcohol, ethylene glycol, acetone.
It is described to obtain particle lithium adsorbent by washing, it further include de- lithium step before washing, the de- lithium uses de- Lithium agent is: hydrochloric acid, sulfuric acid, nitric acid, ammonium persulfate solution, lithium chloride solution or deionized water, and the temperature for taking off lithium is 0-100 DEG C.
The second aspect of the invention provides a kind of particle lithium adsorbent of the method preparation.
The partial size of the particle lithium adsorbent is 0.3-4mm.
Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effects:
The particle lithium adsorbent of the preparation method preparation of particle lithium adsorbent provided by the invention, granule strength height, toughness It is good, it is fitted into non-breakable, dusting in fixed bed or adsorption tower, good hydrophilic property is small with powder adsorbance difference after molding；Technique letter It is single, and the solvent used reuse after rectifying, at low cost, environmental pollution is small, is suitable for industrial applications.
The particle lithium adsorbent of the preparation method preparation of particle lithium adsorbent provided by the invention, is suitable for absorption salt lake halogen Lithium in the lithium-containing solutions such as water, seawater, GEOTHERMAL WATER, solid waste leaching liquid, using multiple polymers as binder, to lithium adsorbent powder Molding granulation is carried out, graininess lithium adsorbent is obtained, granule adsorbent average grain diameter is can be controlled within the scope of 0.3-4.0mm.
Detailed description of the invention
Fig. 1 is particle manganese systems lithium ion sieve stereomicroscope image prepared by the embodiment 1 of different-grain diameter.
A is the particle of average grain diameter 0.840mm；B is the particle of average grain diameter 2.735mm；C is average grain diameter 2.923mm Particle；D is the particle of average grain diameter 3.346mm.
Fig. 2 is the XRD spectra of particle manganese systems lithium ion sieve.
Fig. 3 is the XRD spectra of particle aluminum salt adsorbent.
Fig. 4 is the XRD spectra of particle titanium based lithium-ion sieve.
Fig. 5 is particle manganese systems lithium ion sieve presoma thermogravimetric curve.
Fig. 6 is Li4Mn5O12The curve of adsorption kinetics of particle manganese systems lithium ion sieve prepared by powder and embodiment 1.
Fig. 7 is the adsorption breakthrough curve that fixed bed fills particle lithium adsorbent prepared by embodiment 1.
Fig. 8 is the elution curve that fixed bed fills particle lithium adsorbent prepared by embodiment 1.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this The protection scope of invention.
The average molecular weight of Kynoar used in the embodiment of the present invention is 534000, biochemical purchased from Shanghai Mike woods Science and Technology Ltd.；The molecular weight of polyvinyl alcohol is 31000-500000, purchased from silent winged scientific and technological (China) Co., Ltd of generation that of match； ABS resin model 500P is purchased from DuPont Corporation；The molecular weight of polyvinylpyrrolidone is 50000-60000, purchased from upper The smooth Science and Technology Co., Ltd. of Haitai；Chliorinated polyvinyl chloride model MC250 is purchased from Polyone Corp of the U.S.；The type of polyformaldehyde Number BS090 is purchased from Shanghai Bluestar New Chemical Materials Co., Ltd.；Li4Mn5O12, aluminum salt adsorbent, Li4Ti5O12Powder is self-control.
Li4Mn5O12The preparation method of powder is the following steps are included: by lithium carbonate and manganese carbonate massage that than being 1: It after 2.5 ratio is fully ground, is calcined more than for 24 hours under conditions of temperature is 400 DEG C, obtains Li4Mn5O12Powder.
Aluminum salt adsorbent powder (LiCl2Al (OH)3·nH2The value range of O, n be 0-2) preparation method include with Lower step: being 2.28molL by concentration-1Lithium chloride and concentration be 3.8molL-1Aluminium chloride mixed solution 175mL, with Concentration is 6molL-1, 100mL sodium hydroxide solution be stirred to react, under the conditions of 80 DEG C, using deionized water, with 50mL/g The ratio of powder obtains aluminum salt adsorbent powder after taking off lithium 1h.
Li4Ti5O12The preparation method of powder the following steps are included: be in mass ratio by lithium carbonate and titania powder It after the ratio of 1.05:2.5 is fully ground, is calcined more than for 24 hours under conditions of temperature is 900 DEG C, obtains Li4Ti5O12Powder.
Embodiment 1
5.00g Kynoar and 1.00g polyvinyl alcohol under the conditions of temperature is 80 DEG C, are dissolved in 20mL acetone by normal pressure In, 10g Li is added4Mn5O12Superfine powder and 2.0g sodium chloride powder are uniformly mixed with high-speed homogenization machine stirring 8min Object；The mass ratio of multiple polymers Kynoar and organic solvent is 0.38:1；The matter of pore creating material sodium chloride and organic solvent Amount is than being 0.13:1；The mass ratio of lithium adsorbent or its presoma powder and organic solvent is 0.63:1.
Above-mentioned homogeneous mixture is added drop-wise to volume ratio respectively as the water of 1:1 and mixing for ethyl alcohol using the dropper of different bores It closing in solution 100mL, the mass ratio of homogeneous mixture and solution is 0.02:1, and homogeneous mixture is 0.5m at a distance from solution, The particle manganese systems lithium ion sieve presoma that partial size is 0.8-3.3mm is obtained, by the particle manganese systems lithium ion sieve presoma of acquisition point 0.5molL is not placed in it-1Hydrochloric acid 200ml in, 25 DEG C impregnate 24 hours, washed, obtained not in three times with 100mL deionized water With particle manganese systems lithium ion sieve, that is, particle lithium adsorbent of partial size, partial size 0.8-3.3mm, stereomicroscope image is shown in Fig. 1, Fig. 1 is particle manganese systems lithium ion sieve stereomicroscope image prepared by the embodiment 1 of different-grain diameter.A is average grain diameter 0.840mm Particle；B is the particle of average grain diameter 2.735mm；C is the particle of average grain diameter 2.923mm；D is average grain diameter 3.346mm's Particle, it can be seen from the figure that gained particle manganese systems lithium ion sieve epigranular, and be spherical shape.Gained particle manganese systems lithium from The XRD spectra of son sieve is shown in that Fig. 2, Fig. 2 are the XRD spectra of particle manganese systems lithium ion sieve.It can be seen from the figure that particle after molding Manganese systems lithium ion sieve is still spinel structure.
Embodiment 2
4.50g ABS resin and 2.00g polyvinylpyrrolidone under the conditions of temperature is 50 DEG C, are dissolved in 20mL by normal pressure In chloroform, it is added 9g aluminum salt adsorbent powder LiCl2Al (OH)3With 0.5g sodium chloride powder, stirred with high-speed homogenization machine 8min is mixed to obtain a homogeneous mixture；The mass ratio of multiple polymers and organic solvent is 0.22:1；Pore creating material sodium chloride with it is organic The mass ratio of solvent is 0.017:1；The mass ratio of lithium adsorbent or its presoma powder and organic solvent is 0.3:1.
Above-mentioned homogeneous mixture is added drop-wise to the mixed solution 100mL of water and ethyl alcohol that volume ratio is 1:1 using syringe In, the mass ratio of homogeneous mixture and solution is 0.02:1, and homogeneous mixture is 0.3m at a distance from solution, obtains partial size and is The aluminum salt adsorbent presoma of 1.0mm, is washed in three times with 100mL deionized water, obtains particle aluminum salt adsorbent, that is, particle lithium Adsorbent, partial size 1.0mm.Particle aluminum salt adsorbent XRD spectra is shown in that Fig. 3, Fig. 3 are the XRD spectra of particle aluminum salt adsorbent.From As can be seen that particle aluminum salt adsorbent after molding is still the octahedral structure of aluminium hydroxide in figure.
Embodiment 3
4.5g chliorinated polyvinyl chloride and 1.0g polyformaldehyde under the conditions of temperature is 25 DEG C, are dissolved in 15mL tetrahydro furan by normal pressure In muttering, 10g Li is added4Ti5O12Powder is obtained a homogeneous mixture with high-speed homogenization machine stirring 80min；Multiple polymers with have The mass ratio of solvent is 0.41:1；The mass ratio of lithium adsorbent or its presoma powder and organic solvent is 0.75:1；
Above-mentioned homogeneous mixture is used into extrusion shaping machine extrusion molding, the temperature of extrusion molding is 25 DEG C, extrusion pressure It for 10MPa, is placed in 60 DEG C of air dry ovens and is crushed after drying, obtain the particle titanium based lithium-ion that partial size is 1-2mm and sieve forerunner Body, particle titanium based lithium-ion sieve presoma are placed in 0.5molL-1Hydrochloric acid in 25 DEG C impregnate 120 hours, with 100mL deionization Moisture washs three times, obtains particle titanium based lithium-ion sieve i.e. particle lithium adsorbent, partial size 1-2mm.Particle titanium based lithium-ion sieve XRD spectra is shown in that Fig. 4, Fig. 4 are the XRD spectra of particle titanium based lithium-ion sieve.It can be seen from the figure that particle titanium after molding system lithium Ion sieve is still spinel structure.
Embodiment 4
Particle manganese systems lithium ion sieve prepared by embodiment 1 is dried at 50 DEG C, takes and uses its heat of thermogravimetric analysis steady on a small quantity It is qualitative, see Fig. 5, Fig. 5 is particle manganese systems lithium ion sieve thermogravimetric curve, it can be seen from the figure that it is in 125 DEG C substantially without mistake Weight, illustrates that its thermal stability is good, can be applied to the aqueous solution at various temperature.It is tested using Intelligent testing machine for particle The mechanical strength of the particle manganese systems lithium ion sieve of single diameter about 2.5mm, even if pressure increases to 50N, particle is not still damaged, only It is deformation.
Embodiment 5
Particle manganese systems lithium ion sieve surface prepared by embodiment 1 is blotted with filter paper, weighs the particle m of certain mass1It is (single Position g), while being added a certain amount of deionized water in graduated cylinder and (reading water volume V1(Unit/mL)), by weighed particle loads In cylinder, after particle is completely immersed in water, total volume V is read2(Unit/mL), is subsequently placed into the centrifuge tube of known quality, most Weigh after drying in 50 DEG C of air dry oven (dry particle quality m afterwards2(unit g)) calculates sample with formula 1 and formula 2 The wet density and porosity of grain measure 5 times, the results are shown in Table 1.The porosity for preparing sample as can be seen from Table 1 reaches 79.83%, be conducive to Li+Absorption and desorption.
ρ=m1/(V2-V1) formula 1
P=(m1-m2)/[ρH2O·(V2-V1)] formula 2
In formula: ρ is the wet density of particle, gmL-1；ρH2OFor the density of deionized water, gmL-1；P is pellet pores Rate.
The wet density and porosity of the particle of 1 particle manganese systems lithium ion sieve of table
Serial number Wet density (the gmL of particle-1) Particle porosity (%)
1 1.213 80.94
2 1.229 78.90
3 1.206 81.03
4 1.254 80.07
5 1.218 78.22
Embodiment 6
The ammonia that the lithium chloride of 100mL is added in the particle manganese systems lithium ion sieve for taking 0.3g embodiment 1 to prepare delays solution, and (LiCl is dense Degree is 0.01molL-1, ammonium hydroxide and ammonium chloride concentration are 0.1molL-1) in, measure its curve of adsorption kinetics, and with Li under the same terms4Mn5O12Ion sieve powder (0.1g Li4Mn5O12The ammonia that powder is added to the identical lithium chloride of 100mL delays molten Curve of adsorption kinetics in liquid compares, and sees Fig. 6, Fig. 6 Li4Mn5O12Particle manganese systems lithium ion prepared by powder and embodiment 1 The curve of adsorption kinetics of sieve；After 15 hours, the embodiment of the present invention 1 prepare particle manganese systems lithium ion sieve adsorbance with Li4Mn5O12Powder adsorption amount is not much different.
Embodiment 7
It carries out Dynamic Adsorption-desorption to particle manganese systems lithium ion sieve prepared by embodiment 1 using fixed bed to evaluate, evaluation point For Four processes: 1. adsorption processes are to be passed through certain salt lake bittern in fixed bed from bottom to top with certain flow rate, in adsorption process It is sampled in outlet, the various cation concns in sample；2. deionized water is passed through from bottom to top with certain flow rate after absorption In fixed bed, until outlet solution conductivity and deionized water conductivity are in an order of magnitude；3. desorption process is will 0.5mol·L-1Hydrochloric acid be passed through in fixed bed from bottom to top with certain flow rate, sampled in desorption process in outlet, in sample Various cation concns；4. deionized water is passed through in fixed bed from bottom to top with certain flow rate after desorption, until exporting molten Liquid pH value is greater than 5.
Fixed bed specification is Φ 25mm × 50cm, and adsorption liquid is certain salt lake bittern, and various cation concns are shown in Table 2, absorption Flow velocity is 8mLmin-1When, the adsorption process lithium rate of recovery is 83%, and lithium adsorbance is 1.2mmolg-1, to foreign ion base This is not adsorbed；Using 0.5molL-1Hydrochloric acid, elution flow rate 5mLmin-1When, elution amount is essentially identical with adsorbance, Li in eluent+Concentration highest is concentrated 7 times, and concentration impurity ion significantly reduces, adsorption breakthrough curve and elution curve difference See that Fig. 7 and Fig. 8, Fig. 7 are the adsorption breakthrough curve that fixed bed fills particle lithium adsorbent prepared by embodiment 1, Fig. 8 is fixed bed Fill the elution curve of particle lithium adsorbent prepared by embodiment 1.It can be seen from figure 7 that adsorbent is to Li+Selectivity very It is good, do not adsorb other ions substantially, as can be seen from Figure 8, the Li in desorption liquid+Maximum concentration is more than 300mmolL-1, And Mg2+Maximum concentration be reduced to 50mmolL-1Hereinafter, having achieved the purpose that separating magnesium and lithium.
Various cation concns in 2 salt lake bittern of table
Li+ Na+ K+ Ca2+ Mg2+
Concentration(mmol/L) 50.2 146.7 74.9 3.9 4700
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent thereof.

Claims (10)

1. a kind of preparation method of particle lithium adsorbent, it is characterised in that: the following steps are included:
It in normal pressure, temperature is 10-190 DEG C by lithium adsorbent or its presoma powder, multiple polymers, pore creating material and organic solvent Under conditions of mix, stir 1-120min, obtain a homogeneous mixture；The mass ratio of multiple polymers and organic solvent is (0.01- 10):1；The mass ratio of pore creating material and organic solvent is (0~0.2): 1；Lithium adsorbent or its presoma powder and organic solvent Mass ratio is (0.1~10): 1；
Above-mentioned homogeneous mixture is instilled in solution, the mass ratio of homogeneous mixture and solution is (0.01-0.3): 1, or will be upper It is broken to state homogeneous mixture extrusion molding, obtains particle lithium adsorbent by washing.
2. the preparation method of particle lithium adsorbent according to claim 1, it is characterised in that: the lithium adsorbent or its before Driving body powder is manganese systems lithium ion sieve or its precursor powder, titanium based lithium-ion sieve or its precursor powder, aluminum salt adsorbent powder At least one of end, ferric lithium phosphate precursor powder, preferably at least one of LiMn2O4, aluminum salt adsorbent, lithium titanate.
3. the preparation method of particle lithium adsorbent according to claim 1, it is characterised in that: the multiple polymers are poly- Vinylidene, polypropylene, polyvinyl chloride, chliorinated polyvinyl chloride, polystyrene, polyvinylidene fluoride, gathers inclined two chloroethene at polyethylene Alkene, ABS resin, polyamide, polyformaldehyde, polycarbonate, polyether-ketone, polyether sulfone, polyphenylene oxide, polyurethane, polyvinyl butyral, Polyvinylpyrrolidone, polyacrylic acid, polymethyl methacrylate, polyethylene glycol, polyvinyl alcohol, polyethylene terephthalate At least one of ester.
4. the preparation method of particle lithium adsorbent according to claim 1, it is characterised in that: the pore creating material is chlorination At least one of sodium, potassium chloride, sodium sulphate, potassium sulfate, sodium carbonate, potassium carbonate, sodium nitrate, potassium nitrate.
5. the preparation method of particle lithium adsorbent according to claim 1, it is characterised in that: the organic solvent be benzene, It is toluene, tetrahydrofuran, chloroform, carbon tetrachloride, thionyl chloride, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, complete At least one of vinyl chloride, trichloro ethylene, aromatic hydrocarbons, ethyl acetate, acetone, N-Methyl pyrrolidone.
6. the preparation method of particle lithium adsorbent according to claim 1, it is characterised in that: described by above-mentioned uniform mixing Object instills in solution, and dropwise addition uses method to be added dropwise for dropper, syringe is added dropwise, pumping takes at least one of dropwise addition；
Described to instill above-mentioned homogeneous mixture in solution, homogeneous mixture is 0.1-1m at a distance from solution；
Described to instill above-mentioned homogeneous mixture in solution, solution is water, ethyl alcohol, propyl alcohol, ethylene glycol, at least one in acetone Kind.
7. the preparation method of particle lithium adsorbent according to claim 1, it is characterised in that: described by above-mentioned uniform mixing Object extrusion molding is broken, and the temperature of extrusion molding is 0-200 DEG C, extrusion pressure 0-15MPa.
8. the preparation method of particle lithium adsorbent according to claim 1, it is characterised in that: the washing uses water, second At least one of alcohol, propyl alcohol, ethylene glycol, acetone.
9. the preparation method of particle lithium adsorbent according to claim 1, it is characterised in that: described to be obtained by washing Grain lithium adsorbent further includes de- lithium step before washing, and the de- lithium agent that the de- lithium uses is: hydrochloric acid, sulfuric acid, nitric acid, over cure Acid ammonium solution, lithium chloride solution or deionized water, the temperature for taking off lithium is 0-100 DEG C.
10. a kind of particle lithium adsorbent of the described in any item method preparations of claim 1 to 9.
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