CN102872792A - Composite adsorbing material for removing lithium ions in natural water and preparation method thereof - Google Patents
Composite adsorbing material for removing lithium ions in natural water and preparation method thereof Download PDFInfo
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- CN102872792A CN102872792A CN2012103221153A CN201210322115A CN102872792A CN 102872792 A CN102872792 A CN 102872792A CN 2012103221153 A CN2012103221153 A CN 2012103221153A CN 201210322115 A CN201210322115 A CN 201210322115A CN 102872792 A CN102872792 A CN 102872792A
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Abstract
The invention belongs to the field of water treatment in the environmental protection industry, and particularly relates to a method for preparing a novel composite adsorbing material for removing lithium ions in natural water. The composite adsorbing material is obtained by loading aluminum salt on a lithium ion screen modified by deep sea manganese nodules. According to the invention, the composite adsorbing material is obtained by the following steps of: preparing aluminum hydroxide and lithium hydroxide into aluminum salt, then, modifying the deep sea manganese nodules to obtain the lithium ion screen, combining aluminum slat and the lithium ion screen through a gelatinizing solvent, and finally, settling, washing, filtrating, centrifuging and air drying. The composite adsorbing material for removing the lithium ions in the natural water, provided by the invention, has the characteristics that the selective adsorption capacity on the lithium ions is efficient, the operation the simple, no secondary pollution is caused, recycling is realized, the price is low, and the like. The composite adsorbing material for removing the lithium ions in the natural water, provided by the invention, is simple in technology, low in cost, high in efficiency and beneficial for environmental protection, thereby having higher economic and social benefits in the field of water treatment.
Description
Technical field
[000l] the present invention relates to a kind of composite adsorbing material and affair method processed thereof of removing lithium ion in the natural water body, its body relates to and utilizes aluminium salt to load on a kind of novel material that makes on the lithium ion sieve of making of just having waken up by the deep-sea manganese nodule, belongs to the purifying water process field.
Background technology
Lithium is the alkali metal of at present known the lightest metallic radius minimum, is one of important rare metal of China, be widely used in many necks such as the energy, atomic energy industry, chemical industry space flight or.Because having widely in a lot of fields, lithium and compound thereof use, so the pollution problem of lithium ion more and more is subjected in concern.Lithium ion can polluted underground water and soil, and then pollute fish, family crop etc., destroys human living environment, and then threaten human health.
At present, mainly contain extraction, the precipitation method and absorption method etc. for the method for removing the natural water body lithium ion.Although extraction is simple to operate, cost is not high, but the efficient of removing lithium ion is not high, therefore the method is eliminated gradually, the precipitation method plurality of advantages such as maturation, small investment, processing cost are low, strong adaptability, convenient management, automaticity height that possess skills, be the conventional treatment method of copper-containing wastewater, but can produce copper-contained sludge after processing, also can not produce secondary pollution if mud obtains appropriate processing.And absorption method has selective height, can process the low concentration water body, can realize the characteristics of cleaner production, and technique is simple, considers than additive method larger advantage is arranged from economy and environmental protection supervision.But removing water for existing sorbing material is that the method for lithium ion also has the material can not recycling and have a deficiency of secondary pollution.
The present invention is that a kind of effectively and economic composite adsorbing material the present invention compares with traditional absorption method, has the material reproducible utilization, recycles, the characteristics such as non-secondary pollution.Realize the comprehensive utilization of house refuse, protected environment, widened water and adsorbed the range of choice of giving birth to composite in the process, realized the resource of discarded object, had good Social benefit and economic benefit.
Summary of the invention
[OO05] the objective of the invention is to plant in order to overcome existing technology in material regeneration utilization and the deficiency that recycles, to provide that to remove natural water body be composite adsorbing material of lithium ion and preparation method thereof.The present invention is a kind of novel composite adsorbing material, has the adsorption efficiency height, and simple to operate, cost is low, returns that to change utilization rate large, and tool can be regenerated, the characteristics such as non-secondary pollution.
The objective of the invention is to be achieved through the following technical solutions:
1, raw material screening
Aluminium salt and lithium ion sieve reaction preparation composite: (1) skeleton raw material: aluminium hydroxide, lithium hydroxide: the second raw material is sulfuric acid, hydrochloric acid.(2) the 3rd raw materials are the lithium ion sieve that deep-sea manganese nodule modification becomes.(3) the colloid fcc raw material is organic solvent (ethanol, acetone, methyl alcohol)
2, composite adsorbing material preparation
Add 20%～40% the molten Ji of colloidization in aluminum salt solution, add lithium ion sieve again, the control temperature is 30～60 ℃, hybrid reaction 2～5min, sediment through sedimentation, washing, filtration, centrifugal, wind in making solid material.
Principle of the present invention: aluminum salt adsorbent forms the hole owing to take off the lithium ion face in acid cleaning process, these positions of face are only suitable for lithium ion, so aluminium salt can adsorb lithium ion in a large number under aquation, moreover lithium ion sieve has preferably structural stability and single-minded adsorptivity, can be by make a return journey lithium ion in dewatering of ion exchange, this composite adsorbing material just has larger adsorbance like this.
Application process of the present invention: at the processing natural water body be, according to the concentration of lithium ion in the water, can directly this material be added in the water by 10～20g quality, mix 5～10min, leave standstill 2～5h, supernatant overflows, and mud regularly extracts separation and gets final product.
The invention has the beneficial effects as follows:
(1) the present invention takes full advantage of industrial waste, and raw material is easy to get, and price is more suitable, and the preparation method is simple, is used for water treatment, and 5～10min can reach adsorption equilibrium, and adsorbance is large;
(2) disposal cost of the present invention is cheap, and waste residue can acidifiedly be processed, the recyclable recycling of material;
(3) the present invention is suitable for acidity, neutrality and alkaline water body, and treatment effect is subjected to salinity, temperature shadow to little.
The specific embodiment
1, weighing Al (OH)
3Add scorching the mixing with LiOH, add watery hydrochloric acid and stirring behind reaction 10～20min, make the pH value of mixture supernatant liquor remain on 5～7 letter.Behind pickling 3～5h, the LiCl that it is is removed in the mixture washing, obtain containing the Al (OH) in specific hole
3Crystallization namely is aluminum salt adsorbent;
2, utilize sharp crystalline substance to have and lithium manganese oxide (lithium manganese mass ratio is 1.0) through the synthetic ion sieve presoma of roasting technique (200 ℃ of insulations of roasting technique 2h, 600 ℃ of insulation 6h), then make lithium ion sieve behind the row pickling transformation by to presoma the time;
3, in aluminum salt solution, add 20%～40% colloidization solvent, add again lithium ion sieve, the control temperature is 30～60 ℃, hybrid reaction 2～5min, leave standstill 20～40min, abandoning supernatant washes sediment with water 1～3 time, and sediment is through sedimentation, washing, filtration, centrifugal, the air-dry solid material of making.
Example 1
Weighing AI (OH)
3Add water with LiOH and mix, add watery hydrochloric acid and stirring behind the reaction 10min, the pH value of mixture supernatant liquor is remained between 5.Behind the pickling 3h, mixture is washed the LiCl that removes wherein, obtain containing the Al (0H) in specific hole
3Crystallization namely is aluminum salt adsorbent.Utilize spinelle and lithium manganese oxide (lithium manganese mass ratio is 1.0) through the synthetic ion sieve presoma of roasting technique (200 ℃ of insulations of roasting technique 2h, 600 ℃ of insulation 6h), then by presoma is carried out making lithium ion sieve behind the pickling transformation.The colloidization solvent of adding 20% adds lithium ion sieve again in aluminum salt solution, and the control temperature is 30 ℃, hybrid reaction 2min leaves standstill 20min, abandoning supernatant, wash sediment with water 1 time, sediment is through sedimentation, washing, filtration, centrifugal, the air-dry solid material of making.
Example 2
Weighing AI (OH)
3Add water with LiOH and mix, add watery hydrochloric acid and stirring behind the reaction 20min, the pH value of mixture supernatant liquor is remained between 7.Behind the pickling 5h, mixture is washed the LiCl that removes wherein, obtain containing the AI (OH) in specific hole
3Crystallization namely is aluminum salt adsorbent.Utilize spinelle and lithium manganese oxide (lithium manganese mass ratio is 1.0) through the synthetic ion sieve presoma of roasting technique (200 ℃ of insulations of roasting technique 2h, 600 ℃ of insulation 6h), then by presoma is carried out making lithium ion sieve behind the pickling transformation.The colloidization solvent of adding 40% adds lithium ion sieve again in aluminum salt solution, and the control temperature is 60 ℃, hybrid reaction 5min leaves standstill 40min, abandoning supernatant, wash sediment with water 3 times, sediment is through sedimentation, washing, filtration, centrifugal, the air-dry solid material of making.
Example 3
Weighing AI (OH)
3Add water with LiOH and mix, add watery hydrochloric acid and stirring behind the reaction 15min, the pH value of mixture supernatant liquor is remained between 6.Behind the pickling 4h, mixture is washed the LiCl that removes wherein, obtain containing the AI (OH) in specific hole
3Crystallization namely is aluminum salt adsorbent.Utilize spinelle and and lithium manganese oxide (lithium manganese mass ratio is 1.0) through the synthetic ion sieve presoma of roasting technique (200 ℃ of insulations of roasting technique 2h, 600 ℃ of insulation 6h), then by presoma is carried out making lithium ion sieve behind the pickling transformation.The colloidization solvent of adding 30% adds lithium ion sieve again in aluminum salt solution, and the control temperature is 45 ℃, hybrid reaction 4min, leave standstill the 30min abandoning supernatant, wash sediment with water 2 times, sediment is through sedimentation, washing, filtration, centrifugal, the air-dry solid material of making.
Claims (6)
1. composite absorption material section of removing lithium ion in the natural water body, it is characterized in that: this composite adsorbing material is made aluminium salt take aluminium hydroxide and lithium hydroxide raw material as the skeleton reactant, become lithium ion sieve as the inclusion organic matter take deep-sea manganese nodule modification, be aided with the colloidization solvent, the colloidization solvent is chosen from methyl alcohol, ethanol, acetone.
2. according to the described a kind of composite adsorbing material of removing lithium ion in the natural water body of claim l, it is characterized in that the preparation method of aluminium salt: weighing Al (OH)
3Add water with LiOH and mix, add watery hydrochloric acid and stirring behind reaction 10～20min, the pH value of mixture supernatant liquor is remained between 5～7, behind pickling 3～5h, mixture is washed the LiCl that removes wherein, obtain containing the Al (OH) in specific hole
3Crystallization namely is aluminum salt adsorbent.
3. a kind of composite adsorbing material of removing lithium ion in the natural water body according to claim 1, it is characterized in that deep-sea manganese nodule modification: utilize point product stone and lithium manganese oxide through the synthetic ion sieve presoma of roasting technique, then by presoma is carried out making lithium ion sieve behind the pickling transformation.
4. a kind of composite adsorbing material of removing lithium ion in the natural water body according to claim 3, it is characterized in that: lithium manganese mass ratio is 1.0 in the described lithium manganese oxide.
5. described a kind of composite adsorbing material of removing lithium ion in the natural water body according to claim 3 is characterized in that: 200 ℃ of insulations of described preroast technique 2h, 600 ℃ of insulation 6h.
6. according to the described a kind of preparation method who removes the composite adsorbing material of lithium ion in the natural water body of claim l, the complex method that it is characterized in that aluminium salt and lithium ion sieve: in aluminum salt solution, add 20%～40% colloidization solvent, add again lithium ion sieve, the control temperature is 30～60 ℃, hybrid reaction 2～5min leaves standstill 20～40min, abandoning supernatant, wash sediment l～3 time with water, sediment is through sedimentation, washing, filtration, centrifugal, the air-dry solid material of making.
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| CN105664840A (en) * | 2016-01-12 | 2016-06-15 | 四川天齐锂业股份有限公司 | Modified aluminum salt adsorbent, preparation method and application thereof |
| CN106756106A (en) * | 2017-01-04 | 2017-05-31 | 潍坊学院 | A kind of preparation method of zinc-base lithium ion extraction material |
| CN108046368A (en) * | 2018-01-07 | 2018-05-18 | 天津市职业大学 | Glass-loaded lithium ion sieve filler of a kind of open celled foam and preparation method thereof |
| CN108126651A (en) * | 2018-01-07 | 2018-06-08 | 天津市职业大学 | A kind of lithium ion sieve of fly ash float load and preparation method thereof |
| CN108160024A (en) * | 2018-01-11 | 2018-06-15 | 南京工业大学 | A kind of preparation method of ceramic tube supporter supported ionic sieve |
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| CN108543516A (en) * | 2018-03-31 | 2018-09-18 | 毛强平 | A kind of lithium ion selective absorbent, preparation method and the technique for carrying lithium from brine |
| CN108543514A (en) * | 2018-05-18 | 2018-09-18 | 习贵斌 | A kind of separation method of aluminum salt adsorbent, preparation method and Lithium from Salt Lake Brine |
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| WO2019028174A3 (en) * | 2017-08-02 | 2019-04-11 | Lilac Solutions, Inc. | Ion exchange system for lithium extraction |
| CN110773112A (en) * | 2019-09-25 | 2020-02-11 | 中国科学院青海盐湖研究所 | Modified manganese-based lithium ion sieve and preparation method thereof |
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| CN116917513A (en) * | 2023-05-31 | 2023-10-20 | 广东邦普循环科技有限公司 | Coated lithium manganate lithium ion sieve and preparation method and application thereof |
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Application publication date: 20130116 |