CN105664843B - The method for preparing the hybrid mesoporous adsorption microspheres of micro-nano using red attapulgite stone clay - Google Patents
The method for preparing the hybrid mesoporous adsorption microspheres of micro-nano using red attapulgite stone clay Download PDFInfo
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Abstract
The invention discloses the method for preparing the hybrid mesoporous adsorption microspheres of micro-nano using red attapulgite stone clay, and it is that red attapulgite stone clay is mixed and ground with silicate, 80 140 DEG C of 4h of microwave heating activation 0.5；By obtained solid by solid-to-liquid ratio 1:9.5 are dispersed in aqueous solutions of organic acids, add aqueous metal salt, stir；Obtained suspension is transferred in the hydrothermal reaction kettle of tool tetrafluoro liner, 160 ~ 260 DEG C of 2 ~ 48h of reaction of temperature, room temperature is cooled to 10 DEG C/min speed；Product separating, washing, drying, crush, obtain adsorption microspheres.Rich reserves but grade is relatively low, color and luster is deeper red attapulgite stone clay are obtained the spherical amorphous silicate sorbing material with meso-hole structure by the present invention by processing, product specific surface area is big, pore-size distribution is homogeneous, for antibiotic, mycotoxin, dyestuff, the adsorption and enrichment of heavy metal or removing, there is broad prospect of application in environment remediation, wastewater treatment, feed addictive.
Description
Technical field
The present invention relates to a kind of method for preparing the hybrid mesoporous adsorption microspheres of micro-nano using red attapulgite stone clay, belong to
The deep processing of natural non-metallic ore deposit and technical field of nanometer material preparation.
Background technology
Attapulgite clay（Also referred to as palygorskite or Palygorskite）It is a kind of using attapulgite as the aqueous of main component
Rich zeopan clay mineral, there is nanoclub-like crystal pattern and abundant nano pore, thus there is larger ratio table
Area, show excellent absorption property.China's attapulgite clay resource reserve enriches, and is most found early in Su-Wan area concavo-convex
Rod stone clay ore deposit, in recent years in the area such as Gansu Zhangye, meeting peaceful, Huang Shui, Inner Mongol Hangjin Banner it has also been found that the rich iron of rich reserves is recessed
Convex rod stone clay ore deposit.Taken on a red color due to rich iron in crystalline framework or brick-red, so far still without effectively developed and profit
With resource value can not be transformed into economic value.
In order to lift the performance of attapulgite clay, complicated purification processes are often carried out to attapulgite clay ore deposit, or
To remove quartz sand or opal；Or dolomite and calcite are removed by acidification, to improve purity and performance.
Red attapulgite stone is become white by useful harsh acid treatment method, and then modified, purification processes are used for other field again.Specially
Sharp CN102874826A discloses a kind of method of purification of attapulgite clay, is specifically dispersed in water attapulgite clay
Slurrying, the activation of addition activator, sour removal of impurities, ageing, repeatedly gravitational settling, centrifugation are added, finally obtain purification concave convex rod
Stone clay.Patent CN103738975A discloses a kind of method of purification of attapulgite clay, using slurrying-plus activator-old
The steps such as change-sedimentation-separation improve the purity of attapulgite clay.Purification processes can reduce miscellaneous ore deposit and contain to a certain extent
Amount, the purity of attapulgite is improved, improve performance.However, the complex process of purification, cost are high, water consumption power consumption, activator
Environmental pollution can also be caused.Although with various physical methods（Chinese patent CN104014299A）Or chemical modification method（In
State patent CN102527325A；CN102553519A；CN103611494A；CN102247807A；CN103723785A）Certain
The absorption property of attapulgite is improved in degree, but because red attapulgite stone clay attapulgite content itself is low, composition
Complexity, therefore art methods can not be realized and the nothing of all components in red attapulgite stone clay ore deposit is discarded, be efficiently comprehensive
Close and utilize.
Hydro-thermal method can form new crystal during the course of the reaction or change the form and structure of crystal, at present in kaolinite
Applied in the synthesis of the mineral such as soil, galapectite, serpentine.Patent CN 103191696A disclose a kind of hydro-thermal method and are modified
The method for improving attapulgite absorption property, by high-purity attapulgite（>95%）After hydro-thermal process, specific surface area is from 215
m2/ g increases to 238 m2/ g, it can be lifted to Dye Adsorption performance 26%；Chinese patent CN102974320A discloses a kind of water
It is heat-treated attapulgite（Purity>98%）The method that compound adsorbent is prepared with biomass cellulose, gained adsorbent Pyrogentisinic Acid inhale
Attached rate significantly improves, but this method needs purity>98% attapulgite clay, and attapulgite structure was not being reacted
Change in journey.We also once made minor axis attapulgite major diameter using hydro-thermal method（The A of patent CN 103086392）, but realizing
Attapulgite rod is brilliant in red attapulgite stone clay and associated minerals crystal habit changes, so as to obtain the mesoporous adsorption microspheres of amorphous state
Aspect, at home and abroad also reported at present without any correlative study.
The content of the invention
The purpose of the present invention is：There is provided and a kind of prepare the hybrid mesoporous adsorption microspheres of micro-nano using red attapulgite stone clay
Method, the brick-red attapulgite clay of rich reserves is changed into the mesoporous adsorption microspheres of micro-nano structure amorphous state, opened
While sending out high-efficiency adsorbent, solve the technical bottleneck that efficient absorption material is prepared using low-grade ore or mine tailing, be that China is excellent
The attapulgite clay ore deposit or comprehensive utilization of tailing of gesture open up new way.
The present invention technical solution be：After red attapulgite stone clay is mixed and is fully ground with silicate, 80-
140 DEG C of microwave heating activation 0.5-4h；Then solid-to-liquid ratio 1 is pressed:9.5 are dispersed in the aqueous solution containing organic acid, add metal
The aqueous solution of salt, it is thoroughly mixed uniformly；Obtained suspension is transferred in the hydrothermal reaction kettle of tool tetrafluoro liner, temperature
160 ~ 260 DEG C of 2 ~ 48 h of reaction, then room temperature is cooled to 10 DEG C/min rate programs；Product separating, washing, drying, crush,
Obtain adsorption microspheres.
Wherein, described red attapulgite stone clay is the rich ferrosilicate clay that attapulgite content is 10-40%, color
Pool is brick-red, the associated minerals containing at least one of quartz, dolomite, calcite, montmorillonite and chlorite.
Wherein, the silicate is sodium metasilicate, potassium silicate, potassium metasilicate, sodium potassium silicate, just（Partially）Lithium metasilicate, orthosilicic acid,
Metasilicic acid.
Wherein, silicate quality is the 10%-100% of attapulgite clay quality（Mass fraction）.
Wherein, the metal salt is both magnesium salts and zinc salt composition；Magnesium salts is magnesium chloride, magnesium acetate, magnesium nitrate, ethanol
Magnesium, magnesium sulfate, magnesium stearate；The zinc salt is zinc acetate, zinc chloride, zinc sulfate, zinc nitrate, zinc citrate, zinc oxalate, grape
Saccharic acid zinc；The mass fraction that zinc salt accounts for magnesium salts in composition is 1-25%, and metal salt quality is the 10- of attapulgite clay quality
80%（Mass fraction）.
Wherein, described organic acid is citric acid, benzoic acid, ethylenediamine tetra-acetic acid, oxalic acid, acetic acid, ethanedioic acid, Malaysia
At least one of acid, formic acid, glycolic.
Wherein, the addition of organic acid is the 0.25-2% of attapulgite clay quality（Mass fraction）.
The present invention has advantages below：
1st, the present invention is using the low-quality attapulgite clay of China's rich reserves as raw material, by formula and response parameter
Accurate control, single step reaction is by palygorskite nano rod and quartz, dolomite, calcite, montmorillonite and chlorite associated minerals
Crystal lattice recombination is carried out, is changed into the spherical mesoporous amorphous silicate sorbing material with micro-nano structure, product aperture narrowly distributing,
Specific surface area is 509.86 m2/ g, reach 9.32 times of raw ore specific surface area, to the energy of adsorption of dyestuff, heavy metal and aureomycin
Power improves 227%, 167% and 131% than raw ore respectively.
2nd, the preparation method technique is simple, and process is easily controllable, and product quality is stable, green, adsorption capacity is strong.
3rd, the present invention not only facilitates the higher value application for realizing China's red attapulgite stone clay ore deposit or mine tailing, but also
High-efficiency adsorbent is provided for multiple fields such as environment remediation, wastewater treatment, feeds.
Brief description of the drawings
Fig. 1 is red attapulgite stone clay ore deposit（a）With the adsorption microspheres of embodiment 1（b）And the adsorption microspheres of embodiment 3（c）'s
Digital photograph.
Fig. 2 is the SEM figures of red attapulgite stone clay and the adsorption microspheres of embodiment 1.
Fig. 3 is the XRD spectrum of red attapulgite stone clay and the adsorption microspheres of embodiment 1.
Fig. 4 is the pore size distribution curve of the adsorption microspheres of embodiment 1.
Fig. 5 attapulgite clay raw ore and the adsorption microspheres of embodiment 1 are to aureomycin, heavy metal copper ion and methylene blue
The absorption property of dyestuff.
Embodiment
With reference to embodiment to the present invention technical solution be described further, these embodiments it is not intended that
It is the limitation to technical scheme.
Embodiment 1：4h is ground after 100 g attapulgite clay miberal powders are mixed with 10 g sodium metasilicate, then 140 DEG C of microwaves
Heat 0.5；Obtained product is distributed in the aqueous solution of 800 mL citric acids containing 0.25g, then adds chlorine containing 7.5g
Change the 150mL aqueous solution of magnesium and 2.5g zinc chloride, stir, be transferred in 2 L hydrothermal reaction kettles, 260 DEG C of reactions of temperature
48 h, 10 DEG C/min program are cooled to room temperature；Solid product is separated, is washed with water, is dried in vacuo, ash is obtained after crushing
White sorbing material.
Embodiment 2：Grind 4h after 100 g attapulgite clay miberal powders are mixed with 100 g potassium metasilicates, then 80 DEG C it is micro-
Wave heating handles 4h；Obtained product is distributed in the aqueous solution of 800 mL ethylenediamine tetra-acetic acids containing 2g, then adds and contain 60g
The 150mL aqueous solution of magnesium nitrate and 20g zinc nitrates, is stirred, and is transferred in 2 L hydrothermal reaction kettles, and 160 DEG C of temperature is anti-
2 h are answered, 10 DEG C/min programs are cooled to room temperature；Solid product is separated, is washed with water, is dried in vacuo, is obtained after crushing
Canescence sorbing material.
Embodiment 3：Grind 4h after 100 g attapulgite clay miberal powders are mixed with 50 g sodium potassium silicates, then 100 DEG C it is micro-
Wave heating handles 1h；Obtained product is distributed in the aqueous solution of 800 mL oxalic acid containing 0.5g, then adds acetic acid containing 49.5g
The 150mL aqueous solution of magnesium and 0.5g zinc acetates, is stirred, and is transferred in 2 L hydrothermal reaction kettles, 180 DEG C of reactions 24 of temperature
H, 10 DEG C/min program are cooled to room temperature；Solid product is separated, is washed with water, is dried in vacuo, is obtained after crushing greyish white
Color sorbing material.
Embodiment 4：4h is ground after 100 g attapulgite clay miberal powders are mixed with the positive lithium metasilicates of 100 g, then 140 DEG C
Microwave heating treatment 1h；Obtained product is distributed in the aqueous solution of 800 mL maleic acids containing 2g, then adds chlorination containing 30g
The 150mL aqueous solution of magnesium and 10g zinc chloride, is stirred, and is transferred in 2 L hydrothermal reaction kettles, 200 DEG C of reactions 12 of temperature
H, 10 DEG C/min program are cooled to room temperature；Solid product is separated, is washed with water, is dried in vacuo, is obtained after crushing greyish white
Color sorbing material.
Embodiment 5：4h is ground after 100 g attapulgite clay miberal powders are mixed with 60 g metasilicic acids, then 140 DEG C of microwaves
Heat 4h；Obtained product is distributed in the aqueous solution of 800 mL benzoic acid containing 0.25g, then adds sulfuric acid containing 36g
The 150mL aqueous solution of magnesium and 4g zinc sulfate, is stirred, and is transferred in 2 L hydrothermal reaction kettles, 260 DEG C of reactions 12 of temperature
H, 10 DEG C/min program are cooled to room temperature；Solid product is separated, is washed with water, is dried in vacuo, is obtained after crushing greyish white
Color sorbing material.
The structural characterization and performance of product of the present invention：Pass through SEM（SEM）, X-ray powder diffraction
（XRD）The structure and form of adsorption microspheres are confirmed, the pore structure of adsorption microspheres is tested by BET specific surface area analysis.
It is zonal distribution from accompanying drawing 1 as can be seen that attapulgite raw ore takes on a red color, rich reserves, by hydro-thermal process
Afterwards, canescence sorbing material is obtained.
From accompanying drawing 2 as can be seen that attapulgite is nano bar-shape structure, rod crystalline substance is in state of aggregation, is associated with sheet or granular
Material；After PROCESS FOR TREATMENT of the present invention, rhabdolith disappears, and forms the porose uniform microballoon in surface, microballoon is by big
The nanoparticle aggregation of amount forms.
Accompanying drawing 3 can be seen that attapulgite clay raw ore 2θ =8.38 ° and 2θ Occur respectively at=13.85 ° recessed
Convex rod stone（110）With（200）The characteristic diffraction peak of crystal face, 2θ Occurs stronger Quartz Characteristics peak at=26.68 °, 2θ Occur the characteristic peak of dolomite at=30.09 °, illustrate in attapulgite clay raw ore in addition to attapulgite, also have quartz and
The miscellaneous ore deposit of dolomite；After the method for the invention is handled, attapulgite, quartz and dolomite characteristic peak disappear, and do not have simultaneously
New peak occurs, and illustrates that several materials recombinate the silicate for generating low-crystallinity under thermal and hydric environment.
From accompanying drawing 4 as can be seen that the pore-size distribution of adsorption microspheres peak occurs at 36.59nm and 37.51nm respectively, it was demonstrated that
For mesoporous material.
From accompanying drawing 5 as can be seen that adsorption microspheres are 376 mg/g to the saturated adsorption capacity of aureomycin, concave convex rod is reached
Stone clay raw ore（163 mg/g）2.31 times of adsorbance；The saturated adsorption capacity of heavy metal copper ion is 280.2 mg/g,
Attapulgite clay raw ore adsorbance is reached（105.1 mg/g）2.67 times；To the saturated adsorption capacity of dyestuff methylene blue
For 580.6 mg/g, attapulgite clay raw ore adsorbance is reached（177.5 mg/g）3.27 times.
From subordinate list 1 as can be seen that after the method for the invention is handled, attapulgite clay specific surface area is from former concave convex rod
54.67 m of stone clay2/ g increases to 509.86 m2/g。
Table 1
。
Claims (3)
1. the method for preparing the hybrid mesoporous adsorption microspheres of micro-nano using red attapulgite stone clay, it is characterised in that：It is will be red
After color attapulgite clay is mixed and is fully ground with silicate, 80-140 DEG C of microwave heating activation 0.5-4h；Then solid-liquid is pressed
Than 1:8.0 are dispersed in aqueous solutions of organic acids, add aqueous metal salt, are thoroughly mixed uniformly；The suspension that will be obtained
Liquid is transferred in the hydrothermal reaction kettle of polytetrafluoro liner, 160 ~ 260 DEG C of 2 ~ 48h of reaction of temperature, then is dropped with 10 DEG C/min rate programs
Warm to room temperature；Product separating, washing, drying, crush, obtain adsorption microspheres；The silicate be sodium metasilicate, potassium silicate, partially
One kind in potassium silicate, sodium potassium silicate, positive lithium metasilicate, lithium metasilicate, orthosilicic acid, metasilicic acid；The metal salt is magnesium salts and zinc
Both salt composition；Described organic acid is citric acid, benzoic acid, ethylenediamine tetra-acetic acid, oxalic acid, acetic acid, ethanedioic acid, Malaysia
At least one of acid, formic acid, glycolic；Silicate quality is the 10%-100% of attapulgite clay quality；Organic acid adds
Measure as the 0.25%-2% of attapulgite clay mass fraction.
2. the method according to claim 1 for preparing the hybrid mesoporous adsorption microspheres of micro-nano using red attapulgite stone clay,
It is characterized in that：Described red attapulgite stone clay is the rich ferrosilicate clay that attapulgite content is 10-40%, color and luster
To be brick-red, the associated minerals containing at least one of quartz, dolomite, calcite, montmorillonite and chlorite.
3. the method according to claim 1 for preparing the hybrid mesoporous adsorption microspheres of micro-nano using red attapulgite stone clay,
It is characterized in that：The magnesium salts is magnesium chloride, magnesium acetate, magnesium nitrate, magnesium ethylate, magnesium sulfate, magnesium stearate；The zinc salt is second
Sour zinc, zinc chloride, zinc sulfate, zinc nitrate, zinc citrate, zinc oxalate, zinc gluconate；Zinc salt accounts for the quality of magnesium salts in composition
Fraction is 1-25%, and metal salt combination amount of substance is the 10-80% of attapulgite clay mass fraction.
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| CN107639106B (en) * | 2017-11-15 | 2020-08-11 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Low-grade attapulgite crude ore heavy metal solidified material and method for in-situ remediation of polluted soil by using same |
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| CN114804134B (en) * | 2022-04-12 | 2023-07-25 | 中国科学院广州地球化学研究所 | Mesoporous material preparation method based on clay mineral |
| CN114950346B (en) * | 2022-05-11 | 2023-11-10 | 内蒙古大学 | Efficient dephosphorizing agent prepared from natural calcium-rich mixed clay and preparation method thereof |
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| CN104069801B (en) * | 2013-03-25 | 2016-03-09 | 兰州大学 | The preparation method of attapulgite clay nano stick crystal complex microsphere adsorbent |
| CN103553062A (en) * | 2013-10-30 | 2014-02-05 | 盐城工学院 | Modified ATP (attapulgite) material as well as preparation method and application thereof |
| CN104383873B (en) * | 2014-11-13 | 2016-08-24 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Utilize the method that low-grade attapulgite clay prepares compound adsorbent |
| CN105289470B (en) * | 2015-11-18 | 2018-01-30 | 中国科学院兰州化学物理研究所 | The method that the palygorskite nano composite material of load charcoal is prepared using antibiotic waste water |
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