CN103521197A - Preparation method of light rare earth ion imprinted adsorbent for treating rare earth wastewater - Google Patents
Preparation method of light rare earth ion imprinted adsorbent for treating rare earth wastewater Download PDFInfo
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Abstract
The invention relates to a preparation method of a light rare earth ion imprinted mesoporous molecular sieve adsorbent for absorbing and recycling rare earth ion in wastewater. The preparation method comprises the following steps: firstly, taking tetraethyl orthosilicate as a silicon source and preparing a mesoporous molecular sieve precursor suspension; then inducing aminosilane to couple in the mesoporous molecular sieve precursor suspension by using rare earth imprinted ion, and forming a rare earth ion-aminosilane polymer-mesoporous molecular sieve compound; and finally, removing the rare earth ion in the compound and obtaining a rare earth ion imprinted mesoporous molecular sieve adsorbent. Through absorption materials obtained by the preparation method, the maximum absorption and recovery of the rare earth ion can be realized due to a synergistic effect of a high specific surface area of the molecular sieve and a three-dimensional cavity containing a function group which is specifically bonded with the rare earth imprinted ion.
Description
Technical field
The invention belongs to for the utilization of resources and environmental protection technical field, belong to especially the sorbing material technical field of environmental pollution improvement aspect, that be specifically related to is the preparation method for the treatment of the light rare earth ion trace mesoporous molecular sieve adsorbent of RE waste water.
Background technology
China is not only rare earth resources big country, and has become global rare earth production, outlet and consumption big country.Under the pressure of the progress of Chinese rare earth metallurgy technology and cheap cost, the separated enterprise of external rare-earth smelting closes down in succession, and relevant research also reduces gradually.The rare earth resources of China is with the obvious advantage, for the development of rare-earth industry provides very favourable condition.Since 80 mid-nineties 90s of 20th century, China's rare-earth industry development is very rapid, and has obtained huge achievement.But rare-earth smelting belongs to hydrometallurgy, wastewater flow rate is larger, and waste water has seriously polluted and administer the features such as difficulty, and rare-earth smelting will bring larger environmental problem.Water is resource the most valuable on the earth.Although 71% of earth surface is waters, however wherein only less than 3% be fresh water, and in freshwater resources, only have the less than 1% can be for the mankind directly.The rare earth ions such as the lanthanum containing in the waste water that rare earth ore is discharged after smelting, europium, very large to human health risk, to the traditional processing method of rare earth metal waste water, can not meet and not only reclaim metal but also by the requirement of water reuse.Therefore, improve resource utilization, the rate of recovery, reduce costs, Devoting Major Efforts To Developing and popularization environmental protection novel technique and secondary resource recovery and utilization technology, be the inevitable requirement of rare-earth trade development.
Solve the efficient utilization of rare earth resources and the green of Rare Earth Production, key is that rare earths separation method will have low pollution, feature cheaply efficiently.From clean, green trend analysis of producing, the rare earth ion that the mesoporous molecular sieve adsorbent that utilizes light rare earth ion trace method to prepare adsorbs in recovering rare earth waste water has fine prospect, this is because first mesopore molecular sieve has higher specific area, and more adsorption activity position can be provided the rare earth ion in waste water.Next utilizes the induction of rare earth trace ion, can make the amino functional base on amino silane be fixed up on specific spatial orientation, surface the grafting of amino functional base to mesopore molecular sieve, and amino functional base is distributed at mesopore molecular sieve surface uniform, on mesopore molecular sieve surface, stay the next three-dimensional hole of mating completely and containing with rare earth trace ion with the function base of rare earth trace ion specific binding on space structure.Can optionally be combined with rare earth ion again in this three-dimensional hole, rare earth ion is had to specific recognition effect, thereby greatly improve the adsorption capacity of adsorbent of molecular sieve to rare earth ion.The preparation method of light rare earth ion trace mesoporous molecular sieve adsorbent is simple, and three industrial wastes output is few, is easy to process, and has good social environment benefit and economic benefit.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the light rare earth ion trace mesoporous molecular sieve adsorbent for the treatment of RE waste water.The high-specific surface area that rare earth ion trace mesoporous molecular sieve adsorbent can utilize molecular sieve simultaneously with contain realize to greatest extent rare earth ion with the synergy in the three-dimensional hole of the function base of rare earth trace ion specific binding absorption with separated.
The preparation method of rare earth ion trace mesoporous molecular sieve adsorbent of the present invention is that minute three steps complete.First prepare mesopore molecular sieve forerunner suspension, and then utilize rare earth trace ion induction amino silane to be coupled in mesopore molecular sieve precursor liquid, form rare earth ion-amino silane polymer-mesoporous molecular screen composite.The last rare earth ion of removing again in compound can obtain forming on mesopore molecular sieve surface the three-dimensional hole of the function base with rare earth trace ion specific binding, thereby obtains the rare earth ion trace mesoporous molecular sieve adsorbent with stronger adsorption capacity and certain adsorptive selectivity.
This preparation method specifically comprises the following steps:
(1) under 40 ℃ of conditions by surfactant triblock copolymer P123 (EO
20pO
70eO
20) be dissolved in acid solution, vigorous stirring 10 hours, more slowly drip ethyl orthosilicate (TEOS), continue subsequently vigorous stirring 24h, then move in the autoclave of polytetrafluoroethylsubstrate substrate, under 100 ℃ of conditions, react 10-24h, be cooled to room temperature, obtain mesopore molecular sieve forerunner suspension.The mol ratio of each reactant is: P123:TEOS: acid: H
2o=0.01:1:5.8:136.
(2) the amino silane acidic mixed solution that first configuration contains rare earth ion, then mixed solution is joined under stirring condition in mesopore molecular sieve forerunner suspension, again solution is continued to hydro-thermal reaction 15-24 hour under 80-100 ℃ of condition, cool to room temperature, suction filtration, washing, 100 ℃ are dried 3 hours, obtain pressed powder.The mol ratio of controlling ethyl orthosilicate and amino silane is: 1:0.15-1:0.25, the mol ratio of amino silane and rare earth ion is 1:0.8.
(3) pressed powder obtaining is joined in alcohol and sour mixed solution, the 2-5h that refluxes under 70-100 ℃ of condition, removes surfactant, obtains rare earth ion-amino silane polymer-mesoporous molecular screen composite for 2-3 time.
(4) will obtain rare earth ion-amino silane polymer-mesoporous molecular screen composite joins in acid solution, soak 24 hours, remove rare earth trace ion, can obtain having the rare earth ion trace mesoporous molecular sieve adsorbent of stronger adsorption capacity and certain adsorptive selectivity.
Acid in described step 1 is hydrochloric acid.
Acid solution in described step 2 and 4 is a kind of in hydrochloric acid, nitric acid, sulfuric acid solution.
Described amino silane be 3-aminopropyl trimethoxysilane,
na kind of in-(2-aminoethyl)-3-aminopropyl trimethoxysilane.
Described rare earth ion is a kind of in lanthanum, dysprosium, cerium, praseodymium, neodymium, promethium, samarium, europium plasma.
Described alcohol is a kind of in methyl alcohol or ethanol.
The present invention utilizes mesoporous molecular sieve adsorbent prepared by light rare earth ion trace method to have stronger suction-operated to the rare earth ion of trace in Rare Earth Production waste water, can realize the recycling to Rare Earth Production waste water Rare Earth Ion.Its concrete principle is: it is matrix that this adsorbent be take the adsorbent of molecular sieve synthesizing, and has higher specific area.In addition, utilize the induction of rare earth trace ion, can form on mesopore molecular sieve surface a three-dimensional hole of mating completely and containing with rare earth trace ion with the function base of rare earth trace ion specific binding on space structure.Can optionally be combined with rare earth ion again in this three-dimensional hole, rare earth ion is had to specific recognition effect, thereby greatly improve the adsorption capacity of adsorbent of molecular sieve to rare earth ion.
The inventive method can be prepared the mesoporous molecular sieve adsorbent of rare earth ion trace.Sorbing material prepared by the method with respect to traditional sorbing material have stronger adsorption capacity, specific area large, to features such as the concentration and separation of the rare earth ion in Rare Earth Production waste water are more effective.
The specific embodiment
Embodiment 1:
(1) under 40 ℃ of conditions by 4g surfactant P123 (EO
20pO
70eO
20) be dissolved in (2M) in 120ml hydrochloric acid solution, vigorous stirring 10 hours, slowly drip again 11.3g ethyl orthosilicate (TEOS), continue subsequently vigorous stirring 24h, then move in the autoclave of polytetrafluoroethylsubstrate substrate, under 100 ℃ of conditions, react 24h, be cooled to room temperature, obtain mesopore molecular sieve forerunner suspension.
(2) first 1.5g La
2o
3be dissolved into (2M) in 15ml hydrochloric acid solution, and then the 3-aminopropyl trimethoxysilane that slowly drips 1.2g is prepared the amino silane acidic mixed solution containing lanthanum ion in solution, then mixed solution is joined under stirring condition in mesopore molecular sieve forerunner suspension, again solution is continued to hydro-thermal reaction 15 hours under 100 ℃ of conditions, cool to room temperature, suction filtration, washing, 100 ℃ are dried 3 hours, obtain pressed powder.
(3) pressed powder obtaining is joined in 200ml ethanol+3g 37% hydrochloric acid mixed solution, the 2h that refluxes under 100 ℃ of conditions, repeats 3 times and removes surfactant, obtains lanthanum ion-amino silane polymer-mesoporous molecular screen composite.
(4) will obtain lanthanum ion-amino silane polymer-mesoporous molecular screen composite and join 500ml sulfuric acid solution (2mol/L), soak 24 hours, remove lanthanum ion, can obtain having the rare earth ion trace mesoporous molecular sieve adsorbent of stronger adsorption capacity and certain adsorptive selectivity.
Embodiment 2:
(1) under 40 ℃ of conditions by 2g surfactant P123 (EO
20pO
70eO
20) be dissolved in (2M) in 60ml hydrochloric acid solution, vigorous stirring 10 hours, slowly drip again 6g ethyl orthosilicate (TEOS), continue subsequently vigorous stirring 24h, then move in the autoclave of polytetrafluoroethylsubstrate substrate, under 100 ℃ of conditions, react 15h, be cooled to room temperature, obtain mesopore molecular sieve forerunner suspension.
(2) first 0.65g CeO
2be dissolved into (1.5M) in 10ml hydrochloric acid solution, and then slowly drip 1g's
n-(2-aminoethyl)-3-aminopropyl trimethoxysilane is prepared the amino silane acidic mixed solution containing cerium ion in solution, then mixed solution is joined under stirring condition in mesopore molecular sieve forerunner suspension, again solution is continued to hydro-thermal reaction 24 hours under 80 ℃ of conditions, cool to room temperature, suction filtration, washing, 100 ℃ are dried 3 hours, obtain pressed powder.
(3) pressed powder obtaining is joined in 200ml methyl alcohol+3g 37% hydrochloric acid mixed solution, the 5h that refluxes under 70 ℃ of conditions, repeats 2 times and removes surfactant, obtains cerium ion-amino silane polymer-mesoporous molecular screen composite.
(4) will obtain cerium ion-amino silane polymer-mesoporous molecular screen composite and join 400ml sulfuric acid solution (3mol/L), soak 24 hours, remove cerium ion, can obtain having the rare earth ion trace mesoporous molecular sieve adsorbent of stronger adsorption capacity and certain adsorptive selectivity.
Embodiment 3:
(1) under 40 ℃ of conditions by 3g surfactant P123 (EO
20pO
70eO
20) be dissolved in (2M) in 80ml hydrochloric acid solution, vigorous stirring 10 hours, slowly drip again 8g ethyl orthosilicate (TEOS), continue subsequently vigorous stirring 24h, then move in the autoclave of polytetrafluoroethylsubstrate substrate, under 100 ℃ of conditions, react 20h, be cooled to room temperature, obtain mesopore molecular sieve forerunner suspension.
(2) first 1.6g Nd
2o
3be dissolved into (2M) in 10ml salpeter solution, and then the 3-aminopropyl trimethoxysilane that slowly drips 1.8g is prepared the amino silane acidic mixed solution containing neodymium ion in solution, then mixed solution is joined under stirring condition in mesopore molecular sieve forerunner suspension, again solution is continued to hydro-thermal reaction 20 hours under 90 ℃ of conditions, cool to room temperature, suction filtration, washing, 100 ℃ are dried 3 hours, obtain pressed powder.
(3) pressed powder obtaining is joined in 300ml ethanol+2g 68% hydrochloric acid mixed solution, the 4h that refluxes under 90 ℃ of conditions, repeats 2 times and removes surfactant, obtains neodymium ion-amino silane polymer-mesoporous molecular screen composite.
(4) will obtain neodymium ion-amino silane polymer-mesoporous molecular screen composite and join 400ml salpeter solution (3mol/L), soak 24 hours, remove neodymium ion, can obtain having the rare earth ion trace mesoporous molecular sieve adsorbent of stronger adsorption capacity and certain adsorptive selectivity.
Embodiment 4:
1) under 40 ℃ of conditions by 4g surfactant P123 (EO
20pO
70eO
20) be dissolved in (2M) in 120ml hydrochloric acid solution, vigorous stirring 10 hours, slowly drip again 11.3g ethyl orthosilicate (TEOS), continue subsequently vigorous stirring 24h, then move in the autoclave of polytetrafluoroethylsubstrate substrate, under 100 ℃ of conditions, react 10h, be cooled to room temperature, obtain mesopore molecular sieve forerunner suspension.
(2) first 1.6g Sm
2o
3be dissolved into (3M) in 20ml hydrochloric acid solution, and then slowly drip 1.5g's
n-(2-aminoethyl)-3-aminopropyl trimethoxysilane is prepared the amino silane acidic mixed solution containing samarium ion in solution, then mixed solution is joined under stirring condition in mesopore molecular sieve forerunner suspension, again solution is continued to hydro-thermal reaction 20 hours under 85 ℃ of conditions, cool to room temperature, suction filtration, washing, 100 ℃ are dried 3 hours, obtain pressed powder.
(3) pressed powder obtaining is joined in 300ml methyl alcohol+2g sulfuric acid mixed solution, the 3h that refluxes under 90 ℃ of conditions, repeats 2 times and removes surfactant, obtains samarium ion-amino silane polymer-mesoporous molecular screen composite.
(4) will obtain samarium ion-amino silane polymer-mesoporous molecular screen composite and join 400ml sulfuric acid solution (3mol/L), soak 24 hours, remove lanthanum ion, can obtain having the rare earth ion trace mesoporous molecular sieve adsorbent of stronger adsorption capacity and certain adsorptive selectivity.
Embodiment 5:
(1) under 40 ℃ of conditions by 2g surfactant P123 (EO
20pO
70eO
20) be dissolved in (2M) in 60ml hydrochloric acid solution, vigorous stirring 10 hours, slowly drip again 6g ethyl orthosilicate (TEOS), continue subsequently vigorous stirring 24h, then move in the autoclave of polytetrafluoroethylsubstrate substrate, under 100 ℃ of conditions, react 24h, be cooled to room temperature, obtain mesopore molecular sieve forerunner suspension.
(2) first 1.0g Eu
2o
3be dissolved into (1.6M) in 15ml hydrochloric acid solution, and then the 3-aminopropyl trimethoxysilane that slowly drips 1.2g is prepared the amino silane acidic mixed solution containing europium ion in solution, then mixed solution is joined under stirring condition in mesopore molecular sieve forerunner suspension, again solution is continued to hydro-thermal reaction 24 hours under 80 ℃ of conditions, cool to room temperature, suction filtration, washing, 100 ℃ are dried 3 hours, obtain pressed powder.
(3) pressed powder obtaining is joined in 300ml ethanol+3g68% nitric acid mixed solution, the 5h that refluxes under 80 ℃ of conditions, repeats 2 times and removes surfactant, obtains europium ion-amino silane polymer-mesoporous molecular screen composite.
(4) will obtain europium ion-amino silane polymer-mesoporous molecular screen composite and join 300ml salpeter solution (3mol/L), soak 24 hours, remove europium ion, can obtain having the rare earth ion trace mesoporous molecular sieve adsorbent of stronger adsorption capacity and certain adsorptive selectivity.
Embodiment 6:
(1) under 40 ℃ of conditions by 4g surfactant P123 (EO
20pO
70eO
20) be dissolved in (2M) in 120ml hydrochloric acid solution, vigorous stirring 10 hours, slowly drip again 11.3g ethyl orthosilicate (TEOS), continue subsequently vigorous stirring 24h, then move in the autoclave of polytetrafluoroethylsubstrate substrate, under 100 ℃ of conditions, react 24h, be cooled to room temperature, obtain mesopore molecular sieve forerunner suspension.
(2) first 1.75g Dy
2o
3be dissolved into (2M) in 20ml hydrochloric acid solution, and then the 3-aminopropyl trimethoxysilane that slowly drips 1.2g is prepared the amino silane acidic mixed solution containing dysprosium ion in solution, then mixed solution is joined under stirring condition in mesopore molecular sieve forerunner suspension, again solution is continued to hydro-thermal reaction 24 hours under 80 ℃ of conditions, cool to room temperature, suction filtration, washing, 100 ℃ are dried 3 hours, obtain pressed powder.
(3) pressed powder obtaining is joined in 200ml ethanol+3g 37% hydrochloric acid mixed solution, the 2h that refluxes under 100 ℃ of conditions, repeats 3 times and removes surfactant, obtains dysprosium ion-amino silane polymer-mesoporous molecular screen composite.
(4) will obtain dysprosium ion-amino silane polymer-mesoporous molecular screen composite and join 300ml sulfuric acid solution (1.8mol/L), soak 24 hours, remove dysprosium ion, can obtain having the rare earth ion trace mesoporous molecular sieve adsorbent of stronger adsorption capacity and certain adsorptive selectivity.
Embodiment 7:
(1) under 40 ℃ of conditions by 3g surfactant P123 (EO
20pO
70eO
20) be dissolved in (2M) in 80ml hydrochloric acid solution, vigorous stirring 10 hours, slowly drip again 8g ethyl orthosilicate (TEOS), continue subsequently vigorous stirring 24h, then move in the autoclave of polytetrafluoroethylsubstrate substrate, under 100 ℃ of conditions, react 20h, be cooled to room temperature, obtain mesopore molecular sieve forerunner suspension.
(2) first 1.6g Pr
2o
3be dissolved into (1.8M) in 20ml salpeter solution, and then slowly drip 1.8g's
n-(2-aminoethyl)-3-aminopropyl trimethoxysilane is prepared the amino silane acidic mixed solution containing praseodymium ion in solution, then mixed solution is joined under stirring condition in mesopore molecular sieve forerunner suspension, again solution is continued to hydro-thermal reaction 20 hours under 85 ℃ of conditions, cool to room temperature, suction filtration, washing, 100 ℃ are dried 3 hours, obtain pressed powder.
(3) pressed powder obtaining is joined in 300ml methyl alcohol+2g sulfuric acid mixed solution, the 3h that refluxes under 90 ℃ of conditions, repeats 2 times and removes surfactant, obtains praseodymium ion-amino silane polymer-mesoporous molecular screen composite.
(4) will obtain praseodymium ion-amino silane polymer-mesoporous molecular screen composite and join 400ml sulfuric acid solution (3mol/L), soak 24 hours, remove praseodymium ion, can obtain having the rare earth ion trace mesoporous molecular sieve adsorbent of stronger adsorption capacity and certain adsorptive selectivity.
Embodiment 8:
(1) under 40 ℃ of conditions by 2g surfactant P123 (EO
20pO
70eO
20) be dissolved in (2M) in 60ml hydrochloric acid solution, vigorous stirring 10 hours, slowly drip again 6g ethyl orthosilicate (TEOS), continue subsequently vigorous stirring 24h, then move in the autoclave of polytetrafluoroethylsubstrate substrate, under 100 ℃ of conditions, react 24h, be cooled to room temperature, obtain mesopore molecular sieve forerunner suspension.
(2) first 1.0g Pm
2o
3be dissolved into (1.6M) in 15ml hydrochloric acid solution, and then the 3-aminopropyl trimethoxysilane that slowly drips 1.2g is prepared the amino silane acidic mixed solution containing promethium ion in solution, then mixed solution is joined under stirring condition in mesopore molecular sieve forerunner suspension, again solution is continued to hydro-thermal reaction 24 hours under 80 ℃ of conditions, cool to room temperature, suction filtration, washing, 100 ℃ are dried 3 hours, obtain pressed powder.
(3) pressed powder obtaining is joined in 300ml ethanol+3g68% nitric acid mixed solution, the 5h that refluxes under 80 ℃ of conditions, repeats 2 times and removes surfactant, obtains promethium ion-amino silane polymer-mesoporous molecular screen composite.
(4) will obtain promethium ion-amino silane polymer-mesoporous molecular screen composite and join 300ml salpeter solution (3mol/L), soak 24 hours, remove promethium ion, can obtain having the rare earth ion trace mesoporous molecular sieve adsorbent of stronger adsorption capacity and certain adsorptive selectivity.
Claims (6)
1. for the treatment of the preparation method of the light rare earth ion trace adsorbent of RE waste water, the preparation, the rare earth trace ion induction amino silane that comprise mesopore molecular sieve forerunner suspension are coupled, remove surfactant and rare earth trace ion in mesopore molecular sieve precursor liquid, it is characterized in that this preparation method specifically comprises the following steps:
(1) under 40 ℃ of conditions by surfactant triblock copolymer P123 (EO
20pO
70eO
20) be dissolved in acid solution, vigorous stirring 10 hours, more slowly drip ethyl orthosilicate (TEOS), continue subsequently vigorous stirring 24h, then move in the autoclave of polytetrafluoroethylsubstrate substrate, under 100 ℃ of conditions, react 10-24h, be cooled to room temperature, obtain mesopore molecular sieve forerunner suspension; The amount of substance ratio of each reactant is: P123:TEOS: acid: H
2o=0.01:1:5.8:136;
(2) the amino silane acidic mixed solution that first configuration contains rare earth ion, then mixed solution is joined under stirring condition in mesopore molecular sieve forerunner suspension, again solution is continued to hydro-thermal reaction 15-24 hour under 80-100 ℃ of condition, cool to room temperature, suction filtration, washing, 100 ℃ are dried 3 hours, obtain pressed powder; The mol ratio of controlling ethyl orthosilicate and amino silane is: 1:0.15-1:0.25, and the mol ratio of amino silane and rare earth ion is 1:0.8;
(3) pressed powder obtaining is joined in alcohol and sour mixed solution, the 2-5h that refluxes under 70-100 ℃ of condition, removes surfactant, obtains rare earth ion-amino silane polymer-mesoporous molecular screen composite for 2-3 time;
(4) will obtain rare earth ion-amino silane polymer-mesoporous molecular screen composite joins in acid solution, soak 24 hours, remove rare earth trace ion, can obtain having the rare earth ion trace mesoporous molecular sieve adsorbent of stronger adsorption capacity and certain adsorptive selectivity.
2. the preparation method of the light rare earth ion trace adsorbent for the treatment of RE waste water according to claim 1, is characterized in that: the acid solution described in step (1) is hydrochloric acid.
3. the preparation method of the light rare earth ion trace adsorbent for the treatment of RE waste water according to claim 1, is characterized in that: the acid in the sour mixed solution described in the acidic mixed solution described in step (2) and step (4) is a kind of in hydrochloric acid, nitric acid, sulfuric acid solution.
4. the preparation method of the light rare earth ion trace adsorbent for the treatment of RE waste water according to claim 1, is characterized in that: described amino silane be 3-aminopropyl trimethoxysilane,
na kind of in-(2-aminoethyl)-3-aminopropyl trimethoxysilane.
5. the preparation method of the light rare earth ion trace adsorbent for the treatment of RE waste water according to claim 1, is characterized in that: described rare earth ion is a kind of in lanthanum, dysprosium, cerium, praseodymium, neodymium, promethium, samarium, europium ion.
6. the preparation method of the light rare earth ion trace adsorbent for the treatment of RE waste water according to claim 1, is characterized in that: described alcohol is a kind of in methyl alcohol or ethanol.
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| CN104128168A (en) * | 2014-02-19 | 2014-11-05 | 安徽科技学院 | Preparation method for chromium ion-imprinted silica gel |
| CN106000322B (en) * | 2016-06-02 | 2018-10-09 | 江苏大学 | A kind of preparation method of ion blotting and its adsorption applications to dysprosium ion |
| CN109012639A (en) * | 2018-08-16 | 2018-12-18 | 辽宁大学 | Chitosan silicon based composite material of molybdenum trace and preparation method thereof and the application in recycling rhenium |
| CN109589911A (en) * | 2018-11-23 | 2019-04-09 | 江苏科技大学 | A kind of modified blast furnace slag and its application |
| CN109351332A (en) * | 2018-12-14 | 2019-02-19 | 大连理工大学 | A kind of three-dimensional magnetic graphene/zeolitic material preparation method of highly efficient regeneration absorption rare earth ion |
| WO2021143511A1 (en) * | 2020-01-17 | 2021-07-22 | 武汉赛沣瑞技术有限公司 | N, o type multidentate functional monomer, preparation method therefor and application thereof in ion imprinting material |
| CN114367267A (en) * | 2022-01-19 | 2022-04-19 | 中国科学院赣江创新研究院 | Mesoporous composite material and preparation method and application thereof |
| CN114367267B (en) * | 2022-01-19 | 2023-11-28 | 中国科学院赣江创新研究院 | Mesoporous composite material and preparation method and application thereof |
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