CN109621922A - A kind of monoblock type phenolic resin base lithium ion sieve and its preparation method and application - Google Patents
A kind of monoblock type phenolic resin base lithium ion sieve and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of monoblock type phenolic resin base lithium ion sieves and its preparation method and application, belong to noble metal purification technique field.A kind of preparation method of monoblock type phenolic resin base lithium ion sieve, ball milling after the raw material for being used to prepare mesoporous phenolic resin is mixed with metatitanic acid lithium or mangaic acid lithium powder obtain mixture；Mixture is placed in reaction kettle and carries out curing reaction, then keeps the temperature curing reaction products therefrom in a nitrogen atmosphere, obtains the mesoporous phenolic resin that metatitanic acid lithium or lithium manganate particle are distributed in duct, pickling is to remove Li+, it is washed to neutrality, it is dry, both obtained monoblock type phenolic resin base lithium ion sieve.While the problems such as gained has the Integral lithium ion sieve of hierarchical porous structure, is difficult to separate after solving the absorption of powder formula lithium ion sieve, not easy to operate, lithium ion sieve Li is taken into account+Efficient absorption separating capacity.
Description
Technical field
The present invention relates to a kind of monoblock type phenolic resin base lithium ion sieves and its preparation method and application, and in particular to a kind of
The monoblock type mesoporous phenolic resin base adsorbent that lithium is mentioned for Extracting Lithium from Seawater or salt lake saline, belongs to noble metal purification technique field.
Background technique
In nature, the existence form of elemental lithium is rich and varied, is primarily present in lithium ore, salt lake bittern and seawater
In.It is shown according to United States Geological Survey (USGS) report in 2018, the explored lithium resource total amount in the whole world is more than 53,000,000
Ton, lithium reserves are 16,000,000 tons, wherein being mostly to exist in the form of the liquid lithium resource such as seawater and salt lake bittern.Mesh
Before, it is more mature that ore proposes lithium technology, but energy consumption is high for its recovery process, and at high cost, output is low, and environmental pollution is serious, thus
The economic benefit of exploitation is lower, in addition, the whole world also faces lithium ore resource gradually exhausted problem, these reasons lead to ore
It mentions lithium and has been unable to meet industrial requirement.Therefore, lithium is mentioned from the liquid lithium resource such as seawater and salt lake bittern will become acquisition lithium money
The inevitable choice in source has very big potentiality.
Lithium is mentioned for salt lake bittern, the method used both at home and abroad at present mainly has the precipitation method, solvent extraction, calcining leaching
Method, salting out method, electroosmose process, absorption method etc., but only carbonate precipitation method has put into large-scale industrial application at present.It inhales
Attached method is using to Li+The adsorbent of selective absorption adsorbs Li+, then by Li+Elution, reaches Li+With other foreign ions
Isolated purpose.Therefore its key is sought to Li+Big adsorbance, highly selective, the adsorbent of high circulation utilization rate and low cost.
Two major classes can be divided into according to the property of adsorbent: organic adsorbent and inorganic adsorbent.Wherein organic adsorbent is usually
Cation exchange resin, but it often gets well the adsorption effect of highly charged ions than the adsorption effect of lower valency ion, because
This organic adsorbent is to Li+Selectivity it is lower, industrial applications prospect is small.Inorganic adsorbent mainly has unformed hydroxide
Object adsorbent, layered adsorbent, compound stibate adsorbent and metal oxide ions sieve-type adsorbent.Currently, due to ion
Sieve-type metal oxide is shown to Li+Higher selectivity and biggish adsorption capacity show high lithium separation
Efficiency can obtain the lithium product of high-purity without carrying out further purification operations, become in the salt lake of high Mg/Li ratio
The effective way that lithium resource is extracted in brine and seawater, just has been to be concerned by more and more people, becomes research in recent years
Emphasis has very big commercial application potentiality.
Manganese systems lithium ion sieve although Li with higher+Adsorption capacity, the faster rate of adsorption, however since manganese is with more
Kind of valence state, the chemical property of manganese systems lithium ion sieve is not unusual stabilization, since manganese is from high-valence state in pickling regenerative process
(IV) being reduced into lower valency (II) has the molten damage of biggish manganese.And titanium based lithium-ion sieve is relative to manganese systems lithium ion sieve
For, chemical property is stablized, and molten damage is smaller in pickling regenerative process, therefore its circular regeneration performance is more preferable, the dirt to environment
Dye is smaller, is increasingly becoming the hot spot for mentioning lithium field, but the two is not readily separated after still remaining the absorption of powder formula adsorbent, is operated
It is easy loss in the process, poor fluidity, pressure drop is big, cannot achieve the problems such as pillar operates, therefore be not possible to meet to industrialize and answer
Use demand.And mesoporous phenolic resin, as a kind of monoblock type adsorbent, due to its large specific surface area, pore-size distribution is uniform and is easy to
It is modified, it is increasingly used for adsorption separation process in recent years, but prepares the biography of mesoporous phenolic resin with soft template method
System method is needed using a large amount of solvent, bronsted lowry acids and bases bronsted lowry and highly toxic formaldehyde, from the influence of environment, process safety, the energy
Consumption and product cost etc. consider, limit its large-scale industrial application.
Summary of the invention
It is not necessarily to by soft template method using mechanical ball mill technology in order to solve the above technical problems, the present invention provides one kind
Solvent-induced self assembly mode is prepared for a kind of ordered mesoporous phenolic resin base lithium ion sieve of N doping.When applied to salt
When lake water mentions lithium, achieve it is higher propose lithium effect, be expected to be applied to commercial practice in.
A kind of preparation method of monoblock type phenolic resin base lithium ion sieve, the method is: will be used to prepare mesoporous phenolic aldehyde
Ball milling after the raw material of resin is mixed with metatitanic acid lithium or mangaic acid lithium powder, obtains mixture；Mixture is placed in reaction kettle and is carried out
Curing reaction then keeps the temperature curing reaction products therefrom in a nitrogen atmosphere, obtains and metatitanic acid lithium or mangaic acid are distributed in duct
The mesoporous phenolic resin of lithium particle, pickling is to remove Li+, it is washed to neutrality, it is dry, both obtain monoblock type phenolic resin base lithium ion
Sieve.
In above-mentioned technical proposal, the monoblock type phenolic resin base lithium ion sieve retrodeviates lithium titanate or mangaic acid through pickling processes
Li in lithium particle+Removing forms H2TiO3Or HMn2O4Particle.
In above-mentioned technical proposal, the raw material for being used to prepare mesoporous phenolic resin is phenolic compound, hexa-methylene four
Amine, template, wherein the phenolic compound is resorcinol, hydroquinone, catechol；The template be P123 or
The block copolymer of person's P127 class.
Further, the metatitanic acid lithium or mangaic acid lithium powder are the 1~200% of phenolic compound quality.
Further, the metatitanic acid lithium or mangaic acid lithium powder are nano-metatitanic acid lithium or nanometer lithium manganate powder.
Further, the phenolic compound, hexa, template mass ratio be 10:3:25.
In above-mentioned technical proposal, the curing reaction carries out in hydrothermal reaction kettle, and 100~200 DEG C of reaction temperature, reaction
Time is for 24 hours.
Further, it is preferable to the curing reaction carries out in hydrothermal reaction kettle, and 160 DEG C of reaction temperature, the reaction time
24h。。
In above-mentioned technical proposal, the curing reaction products therefrom 200~400 DEG C of 1~10h of heat preservation in a nitrogen atmosphere.
In above-mentioned technical proposal, under room temperature, the mesoporous phenolic aldehyde tree of metatitanic acid lithium or lithium manganate particle will be distributed in duct
Rouge is placed in 0.5M hydrochloric acid to impregnate carries out pickling for 24 hours, by the Li in metatitanic acid lithium or lithium manganate particle+Sufficiently elution；By pickling
Resulting materials are washed with deionized to neutrality afterwards, 60 DEG C of vacuum drying 12h.
It is described whole it is a further object of the present invention to provide monoblock type phenolic resin base lithium ion prepared by the above method sieve
Body formula phenolic resin base lithium ion sifter device has the porous three-dimensional network structure of perforation, and specific surface area is in 50~1000m2/ g it
Between；H2TiO3Or HMn2O4Even particulate dispersion is inside phenolic resin duct.
It is yet another object of the invention to provide sieved using above-mentioned monoblock type phenolic resin base lithium ion in seawater or salt lake saline
In propose the method for lithium.
A method of lithium being mentioned in seawater or salt lake saline, specifically: at 30 DEG C, by the monoblock type phenolic resin base lithium
Ion sieve is placed in seawater or salt lake saline containing lithium ion, while stirring seawater or salt lake saline.
The dosage of monoblock type phenolic resin base lithium ion of the present invention sieve can according in solution to be processed lithium ion it is dense
Degree determines that in general, the dosage of the more big then monoblock type phenolic resin base lithium ion sieve of concentration is bigger, but has no spy to its dosage
It does not limit.Amount of solution to be processed is big and can be by the side that repeatedly handles when the dosage of monoblock type phenolic resin base lithium ion sieve is few
Formula carries out.Further, the monoblock type phenolic resin base lithium ion sieve and the mass ratio of seawater or salt lake saline are 10~30%.
The method of the present invention that lithium is mentioned in seawater or salt lake saline includes the steps that regeneration: will adsorb the whole of lithium ion
Body formula phenolic resin base lithium ion sieve carries out pickling to remove Li+, it is washed to neutrality, it is dry, both obtain monoblock type phenolic resin base
Lithium ion sieve.
Further, the pickling are as follows: the mesoporous phenolic resin of metatitanic acid lithium or lithium manganate particle will be distributed in duct
It is placed in 0.5M hydrochloric acid to impregnate and carries out pickling for 24 hours, by the Li in metatitanic acid lithium or lithium manganate particle+Sufficiently elution.
The invention has the benefit that the present invention is by the pore structure and lithium ion sieve excellent based on phenolic resin adsorbent
To Li+The advantages that efficient absorption separating property and mechanical ball mill self assembly mode simple process, utilizes machine by soft template method
It is compound with phenolic resin that powder is proposed lithium agent by the mode of tool ball milling self assembly, and a kind of entirety with hierarchical porous structure is prepared
While the problems such as formula lithium ion sieve is difficult to separate after solving the absorption of powder formula lithium ion sieve, not easy to operate, lithium ion is taken into account
Sieve Li+Efficient absorption separating capacity.Preparation method not only simple process, avoids a large amount of solvents, and soda acid and formaldehyde make
With, additionally it is possible to expand to the preparation of other kinds of porous material.
Detailed description of the invention
Fig. 1 is to be not added with a nanometer Li in embodiment 12TiO3Monoblock type phenolic resin electromicroscopic photograph；
Fig. 2 is that additive metatitanic acid lithium and resorcinol ratio are monoblock type phenolic aldehyde tree prepared by 1:2 in embodiment 1
Rouge/Li2TiO3The electromicroscopic photograph of composite material；
Fig. 3 is three kinds of different monoblock type phenolic resin/H described in Examples 1 and 22TiO3Lithium ion sieve mentions lithium adsorption curve.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
Nano-metatitanic acid lithium (Li2TiO3) preparation: weigh 11.56g LiOHH2O is dissolved in 100mL water, then plus
Enter 10g nano-TiO2, stir and be allowed to be uniformly dispersed, 160 DEG C of constant temperature of water heating kettle are then transferred to for 24 hours, then by liquid mixture
After being evaporated at 80 DEG C, 4h is calcined under 650 DEG C of air atmospheres, that is, nano-metatitanic acid lithium (Li is prepared2TiO3)。
Monoblock type phenolic resin/Li2TiO3The preparation of composite material: 1g resorcinol, 2.5g F127 are weighed
(EO106PO70EO106), 0.3g hexa, 0.5g nanometers of Li2TiO3Ground and mixed is carried out, ball grinder ball is then transferred to
Grind 2h, solid mixture be transferred in water heating kettle 160 DEG C of solidifications, constant temperature for 24 hours, the nitrogen gas by obtained product at 350 DEG C
Keeping the temperature 3h under atmosphere and removing template agent method F127 is to obtain monoblock type phenolic resin/Li2TiO3Composite material (is named as LTO/m-P=
1:2, Fig. 2).
Preparation is not added with a nanometer Li simultaneously2TiO3Monoblock type phenolic resin: weigh 1g resorcinol, 2.5g F127
(EO106PO70EO106), 0.3g hexa carries out ground and mixed, is then transferred to ball grinder ball milling 2h, solid is mixed
Object is transferred to 160 DEG C of solidifications in water heating kettle, and constant temperature keeps the temperature 3h under 350 DEG C of nitrogen atmosphere for 24 hours, by obtained product and removes mould
Plate agent method F127 obtains monoblock type phenolic resin and (is named as PR, Fig. 1, is not added with Li2TiO3)。
Monoblock type phenolic resin/H2TiO3The preparation of lithium ion sieve: by phenolic resin/Li of above-mentioned preparation2TiO3Composite wood
Material is placed in 100mL 0.5M hydrochloric acid to be impregnated for 24 hours under room temperature, makes Li2TiO3In Li+The material after pickling is used in sufficiently elution
Deionized water is washed to neutrality, and 60 DEG C of vacuum drying 12h obtain monoblock type phenolic resin/H2TiO3Lithium ion sieve.
By 10mg monoblock type phenolic resin/H2TiO3The LiCl that 10mL difference initial concentration pH=11 is added in lithium ion sieve is molten
It in liquid, is stirred at 30 DEG C, reaches balance (time that absorption reaches balance is measured by adsorption dynamics adsorption kinetics), take a small amount of solution mistake
Filter, using Li in ICP-AES measurement solution+Concentration.Test discovery, monoblock type phenolic resin/H2TiO3Compound lithium ion sieve
Adsorption dynamics adsorption kinetics is compared to pure powder formula nanometer H2TiO3The adsorption dynamics adsorption kinetics of lithium ion sieve is not much affected, still
(about 8h) adsorption equilibrium can be reached within the faster time, and equilibrium adsorption capacity reaches 28.8mg/g, reaches a nanometer H2TiO3Lithium
The 79% of ion sieve equilibrium adsorption capacity (36.4mg/g), it is close with load efficiency.This illustrate preparation monoblock type phenolic resin/
H2TiO3Compound lithium ion sieve equilibrium adsorption capacity be declined slightly, but decline degree it is little, adsorption effect substantially with pure powder nanometer
H2TiO3Lithium ion sieve is suitable, can substitute pure powder nanometer H substantially2TiO3Lithium ion sieve.At the same time, monoblock type phenolic aldehyde tree
Rouge/H2TiO3Lithium ion sieve has excellent recuperability energy, recoverable, and pure powder nanometer H2TiO3Lithium ion sieve is then
It can not almost recycle.
Embodiment 2
It is identical as 1 the method for embodiment, unlike: Li2TiO3It is respectively 1:1 and 2:1, institute with resorcinol ratio
Obtain phenolic resin/Li2TiO3Composite material is respectively designated as LTO/m-P=1:1 and LTO/m-P=2:1.Sample is found through experiments that
The maximal absorptive capacity of product is respectively 17.51mg/g and 29.55mg/g.Relative to pure powder H2TiO3Ion sieve adsorbant, phenolic aldehyde tree
Rouge/H2TiO3The maximal absorptive capacity of compound lithium ion sieve shows that material microporous mesoporous structure abundant can there is no obvious decaying
Sufficiently exposure H2TiO3Adsorption site, reduce ion sieve adsorption capacity loss (Fig. 3).
Embodiment 3
It is identical as 1 the method for embodiment, unlike: nanometer lithium manganate (LiMn2O4) preparation: in 70mL0.1M
0.85g potassium permanganate is added in the solution of LiOH, stirring 30min to potassium permanganate is completely dissolved, and 0.395mL third is then added
Ketone persistently stirs 3h, then mixed solution is transferred in water heating kettle, 190 DEG C of hydro-thermals, constant temperature 5h.Products therefrom is rushed repeatedly
PH is washed till as neutrality, nanometer lithium manganate (LiMn is prepared in 80 DEG C of dry 12h2O4)。
Prepared monoblock type phenolic resin/HMn2O4Lithium ion sieve shows excellent absorption property, maximum adsorption
Amount is up to 30.1mg/g, time of equilibrium adsorption about 6h, and the adsorbance of 25.2mg/g is still able to maintain after circular regeneration 6 times, maintains
The 90% of initial adsorption amount, excellent circular regeneration performance is shown.
Claims (10)
1. a kind of preparation method of monoblock type phenolic resin base lithium ion sieve, it is characterised in that:
Ball milling after the raw material for being used to prepare mesoporous phenolic resin is mixed with metatitanic acid lithium or mangaic acid lithium powder, obtains mixture；It will
Mixture, which is placed in reaction kettle, carries out curing reaction, then keeps the temperature curing reaction products therefrom in a nitrogen atmosphere, obtains duct
In the mesoporous phenolic resin of metatitanic acid lithium or lithium manganate particle is distributed with, pickling is to remove Li+, it is washed to neutrality, it is dry, both
Monoblock type phenolic resin base lithium ion sieve.
2. according to the method described in claim 1, it is characterized by: the raw material for being used to prepare mesoporous phenolic resin is phenols chemical combination
Object, hexa, template, wherein the phenolic compound is resorcinol, hydroquinone, catechol；The mould
Plate agent is P123 P127 based block copolymer.
3. according to the method described in claim 2, it is characterized by: the metatitanic acid lithium or mangaic acid lithium powder are phenolic compound
The 1~200% of quality.
4. according to the method described in claim 2, it is characterized by: the phenolic compound, hexa, template
Mass ratio is 10:3:25.
5. according to the method described in claim 1, it is characterized by: the curing reaction carries out in hydrothermal reaction kettle, reaction
100~200 DEG C of temperature, the reaction time is for 24 hours.
6. according to the method described in claim 1, it is characterized by: the curing reaction products therefrom in a nitrogen atmosphere 200
~400 DEG C of 1~10h of heat preservation.
7. according to the method described in claim 1, it is characterized by: metatitanic acid lithium or mangaic acid will be distributed in duct under room temperature
The mesoporous phenolic resin of lithium particle is placed in 0.5M hydrochloric acid to impregnate carries out pickling for 24 hours, will be in metatitanic acid lithium or lithium manganate particle
Li+Sufficiently elution；Resulting materials after pickling are washed with deionized to neutrality, 60 DEG C of vacuum drying 12h.
8. monoblock type phenolic resin base lithium ion sieve, feature made from any one of claim 1~7 claim the method
Be: the monoblock type phenolic resin base lithium ion sifter device has a porous three-dimensional network structure of perforation, specific surface area 50~
1000m2Between/g；H2TiO3Or HMn2O4Even particulate dispersion is inside phenolic resin duct.
9. a kind of method for mentioning lithium in seawater or salt lake saline, it is characterised in that: at 30 DEG C, by monoblock type described in claim 8
Phenolic resin base lithium ion sieve is placed in seawater or salt lake saline containing lithium ion, while stirring seawater or salt lake saline.
10. according to the method described in claim 9, it is characterized by: the method includes regenerating: will adsorb lithium from
The monoblock type phenolic resin base lithium ion sieve of son carries out pickling to remove Li+, it is washed to neutrality, it is dry, both obtain monoblock type phenolic aldehyde
Resin base lithium ion sieve.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110729476A (en) * | 2019-10-22 | 2020-01-24 | 中国科学院宁波材料技术与工程研究所 | Pseudo-capacitance composite high-capacity lithium manganate positive electrode material and preparation method thereof, and lithium ion battery |
| CN115069209A (en) * | 2022-06-27 | 2022-09-20 | 天津科技大学 | Titanium-based lithium ion sieve inorganic composite adsorption lithium extraction material and preparation method thereof |
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| 赵祎: "整体式酚醛树脂基锂离子筛的制备及其分离性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110729476A (en) * | 2019-10-22 | 2020-01-24 | 中国科学院宁波材料技术与工程研究所 | Pseudo-capacitance composite high-capacity lithium manganate positive electrode material and preparation method thereof, and lithium ion battery |
| CN110729476B (en) * | 2019-10-22 | 2021-08-17 | 中国科学院宁波材料技术与工程研究所 | Pseudo-capacitance composite high-capacity lithium manganate positive electrode material and preparation method thereof, and lithium ion battery |
| CN115069209A (en) * | 2022-06-27 | 2022-09-20 | 天津科技大学 | Titanium-based lithium ion sieve inorganic composite adsorption lithium extraction material and preparation method thereof |
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