CN105664843A - Method for preparing micro-nano hybrid mesoporous adsorbing microspheres by utilizing red attapulgite clay - Google Patents
Method for preparing micro-nano hybrid mesoporous adsorbing microspheres by utilizing red attapulgite clay Download PDFInfo
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- 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
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
Abstract
The invention discloses a method for preparing micro-nano hybrid mesoporous adsorbing microspheres by utilizing red attapulgite clay. The method comprises the steps of mixing the read attapulgite clay with silicate, and grinding, performing microwave heating at 80 to 140 DEG C, and activating for 0.5 to 4h; dispersing the obtained solid into an organic acid aqueous solution according to the solid-to-liquid ratio of 1 to 9.5, then adding a metal salt water solution, and uniformly stirring; transferring the obtained suspension liquid into a hydrothermal reactor provided with a tetrafluoroethylene liner, reacting at temperature of 160 to 260 DEG C for 2 to 48h, and cooling to the normal temperature at the speed of 10 DEG C/min; performing separating, washing, drying and smashing on a product to obtain the adsorbing microspheres. According to the method disclosed by the invention, the red attapulgite clay with abundant reserves, low grade and deep color and luster is subjected to treatment to obtain a spherical amorphous silicate adsorbing material with the mesoporous structure, and a product is large in specific surface area, uniform in pore diameter distribution, can be used for adsorption and enrichment or desorption of antibiotic, mycotoxin, dye and heavy metal, and has a wide application prospect in environmental restoration, wastewater treatment and feed additives.
Description
Technical field
The present invention relates to a kind of method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano, 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 Paligorskite or Palygorskite) be a kind of with attapulgite be main component containing Shuifu County's zeopan clay mineral, there is nanoclub-like crystal pattern and abundant nano pore, thus there is bigger specific surface area, show the absorption property of excellence. China's attapulgite clay resource reserve enriches, and finds attapulgite clay ore deposit as far back as Su-Wan area, in recent years in Zhangye, Gansu, can the area such as peaceful, Huang Shui, Inner Mongol Hangjin Banner it have also been found that the rich ferrum attapulgite clay ore deposit of rich reserves. Taking on a red color or brick-red due to ferrum rich in crystalline framework, so far still without obtaining effective development and utilization, resource value can not be transformed into economic worth.
In order to promote the serviceability of attapulgite clay, often attapulgite clay ore deposit is carried out complicated purification processes, or to remove quartz sand or opal; Or dolomite and calcite is removed by acidification, to improve purity and serviceability. Also red attapulgite stone is become white by the acid treatment method of useful harshness, and then modified, purification processes is used for other field again. Patent CN102874826A discloses the method for purification of a kind of attapulgite clay, specifically attapulgite clay is dispersed in water slurrying, adds activator activation, adds acid remove impurity, ageing, gravitational settling, repeatedly centrifugation, finally obtain purification attapulgite clay. Patent CN103738975A discloses the method for purification of a kind of attapulgite clay, adopts the steps such as slurrying-Jia activator-ageing-sedimentation-separation to improve the purity of attapulgite clay. Purification processes can reduce assorted mineral content to a certain extent, improves the purity of attapulgite, improves serviceability. But, the complex process of purification, cost are high, water consumption power consumption, and activator also can cause environmental pollution. Although with various physical methods (Chinese patent CN104014299A) or chemical modification method (Chinese patent CN102527325A;CN102553519A; CN103611494A; CN102247807A; CN103723785A) improve the absorption property of attapulgite to a certain extent, but owing to red attapulgite stone clay attapulgite content own is low, complicated component, therefore art methods can not realize the nothing of all components in red attapulgite stone clay ore deposit is discarded, high-efficiency comprehensive utilization.
Hydro-thermal method can form new crystal in course of reaction or change form and the structure of crystal, has obtained application at present in the synthesis of the mineral such as Kaolin, galapectite, serpentine. Patent CN103191696A discloses a kind of hydro-thermal method and modifiies the method improving attapulgite absorption property, by high-purity attapulgite (> 95%) after hydrothermal treatment consists, specific surface area is from 215m2/ g increases to 238m2/ g, it is possible to promote dye adsorption performance 26%; The method that Chinese patent CN102974320A discloses a kind of hydrothermal treatment consists attapulgite (purity > 98%) and biomass cellulose prepares compound adsorbent, gained adsorbent Pyrogentisinic Acid's adsorption rate significantly improves, but the method needs purity > attapulgite clay of 98%, and also attapulgite structure does not change in course of reaction. We also once utilized hydro-thermal method to make minor axis attapulgite major diameter (patent CN103086392A), but in realizing red attapulgite stone clay, attapulgite rod is brilliant changes with associated minerals crystal habit, thus obtaining the mesoporous adsorption microspheres aspect of amorphous state, at home and abroad report but without any correlational study at present.
Summary of the invention
It is an object of the invention to: a kind of method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano is provided, the brick-red attapulgite clay of rich reserves is changed into there is the mesoporous adsorption microspheres of micro-nano structure amorphous state, while exploitation high-efficiency adsorbent, solving to utilize low-grade ore or mine tailing to prepare the technical bottleneck of efficient absorption material, new way is opened up in attapulgite clay ore deposit or comprehensive utilization of tailing for China's advantage.
The technical solution of the present invention is: after red attapulgite stone clay is mixed with silicate and is fully ground, 80-140 DEG C of microwave heating activation 0.5-4h; Then it is dispersed in containing, in organic aqueous acid, adding the aqueous solution of slaine, be sufficiently stirred for mix homogeneously by solid-to-liquid ratio 1:9.5; The suspension obtained is proceeded in the hydrothermal reaction kettle of tool tetrafluoro liner, temperature 160 ~ 260 DEG C reaction 2 ~ 48h, then it is cooled to room temperature with 10 DEG C/min rate program; Product separating, washing, drying, pulverizing, obtain adsorption microspheres.
Wherein, described red attapulgite stone clay is attapulgite content is the rich ferrosilicate clay of 10-40%, and color and luster is brick-red, containing associated minerals at least one in quartz, dolomite, calcite, montmorillonite and chlorite.
Wherein, described silicate is sodium silicate, potassium silicate, potassium metasilicate, sodium potassium silicate, just (partially) Lithium metasilicate, orthosilicic acid, metasilicic acid.
Wherein, silicate quality is the 10%-100%(mass fraction of attapulgite clay quality).
Wherein, described slaine is both magnesium salt and zinc salt compositions; Magnesium salt is magnesium chloride, magnesium acetate, magnesium nitrate, Diethoxymagnesium, magnesium sulfate, magnesium stearate; Described zinc salt is zinc acetate, zinc chloride, zinc sulfate, zinc nitrate, zinc citrate, zinc oxalate, zinc gluconate; In compositions, zinc salt accounts for the mass fraction of magnesium salt is 1-25%, and slaine quality is the 10-80%(mass fraction of attapulgite clay quality).
Wherein, described organic acid is at least one in citric acid, benzoic acid, ethylenediaminetetraacetic acid, oxalic acid, acetic acid, ethanedioic acid, maleic acid, formic acid, glycolic.
Wherein, organic acid addition is the 0.25-2%(mass fraction of attapulgite clay quality).
The invention have the advantages that
1, the present invention is with the low-quality attapulgite clay of China's rich reserves for raw material, by the accurate control to formula and response parameter, palygorskite nano rod and quartz, dolomite, calcite, montmorillonite and chlorite associated minerals are carried out crystal lattice recombination by single step reaction, it is changed into the spherical mesoporous amorphous silicate adsorbing material with micro-nano structure, product aperture narrowly distributing, specific surface area is 509.86m2/ g, reaches 9.32 times of raw ore specific surface area, and than raw ore, the absorbability of dyestuff, heavy metal and chlortetracycline is improved 227%, 167% and 131% respectively.
2, this preparation method technique is simple, and process is easily controllable, constant product quality, environmental protection, high adsorption capacity.
3, the present invention not only facilitates the higher value application realizing China's red attapulgite stone clay ore deposit or mine tailing, but also provides high-efficiency adsorbent for multiple fields such as environment remediation, wastewater treatment, feedstuffs.
Accompanying drawing explanation
Fig. 1 is red attapulgite stone clay ore deposit (a) and the digital photograph of embodiment 1 adsorption microspheres (b) and embodiment 3 adsorption microspheres (c).
Fig. 2 is the SEM figure of red attapulgite stone clay and embodiment 1 adsorption microspheres.
Fig. 3 is the XRD figure spectrum of red attapulgite stone clay and embodiment 1 adsorption microspheres.
Fig. 4 is the pore size distribution curve of embodiment 1 adsorption microspheres.
Fig. 5 attapulgite clay raw ore and embodiment 1 adsorption microspheres absorption property to chlortetracycline, heavy metal copper ion and methylene blue dye.
Detailed description of the invention
Below in conjunction with embodiment, the technical solution of the present invention being described further, these embodiments are not to be construed as the restriction to technical scheme.
Embodiment 1: grind 4h, then 140 DEG C of microwave heating treatment 0.5 with 10g sodium silicate after being mixed by 100g attapulgite clay breeze; The product obtained is distributed to 800mL containing in 0.25g Fructus Citri Limoniae aqueous acid, it is subsequently adding the 150mL aqueous solution containing 7.5g magnesium chloride and 2.5g zinc chloride, stirs, proceed in 2L hydrothermal reaction kettle, temperature 260 DEG C reaction 48h, 10 DEG C/min programmed cooling is to room temperature; Solid product is separated, washes with water, vacuum drying, obtain canescence adsorbing material after pulverizing.
Embodiment 2: grind 4h, then 80 DEG C of microwave heating treatment 4h with 100g potassium metasilicate after being mixed by 100g attapulgite clay breeze; The product obtained is distributed in the 800mL aqueous solution containing 2g ethylenediaminetetraacetic acid, it is subsequently adding the 150mL aqueous solution containing 60g magnesium nitrate and 20g zinc nitrate, stirs, proceed in 2L hydrothermal reaction kettle, temperature 160 DEG C reaction 2h, 10 DEG C/min programmed cooling is to room temperature; Solid product is separated, washes with water, vacuum drying, obtain canescence adsorbing material after pulverizing.
Embodiment 3: grind 4h, then 100 DEG C of microwave heating treatment 1h with 50g sodium potassium silicate after being mixed by 100g attapulgite clay breeze; The product obtained is distributed to 800mL containing in 0.5g grass aqueous acid, it is subsequently adding the 150mL aqueous solution containing 49.5g magnesium acetate and 0.5g zinc acetate, stirs, proceed in 2L hydrothermal reaction kettle, temperature 180 DEG C reaction 24h, 10 DEG C/min programmed cooling is to room temperature;Solid product is separated, washes with water, vacuum drying, obtain canescence adsorbing material after pulverizing.
Embodiment 4: grind 4h, then 140 DEG C of microwave heating treatment 1h with the positive Lithium metasilicate of 100g after being mixed by 100g attapulgite clay breeze; The product obtained is distributed to 800mL containing in the aqueous acid of 2g Malaysia, it is subsequently adding the 150mL aqueous solution containing 30g magnesium chloride and 10g zinc chloride, stirs, proceed in 2L hydrothermal reaction kettle, temperature 200 DEG C reaction 12h, 10 DEG C/min programmed cooling is to room temperature; Solid product is separated, washes with water, vacuum drying, obtain canescence adsorbing material after pulverizing.
Embodiment 5: grind 4h, then 140 DEG C of microwave heating treatment 4h with 60g metasilicic acid after being mixed by 100g attapulgite clay breeze; The product obtained is distributed to 800mL containing in the benzoic aqueous solution of 0.25g, it is subsequently adding the 150mL aqueous solution containing 36g magnesium sulfate and 4g zinc sulfate, stirs, proceed in 2L hydrothermal reaction kettle, temperature 260 DEG C reaction 12h, 10 DEG C/min programmed cooling is to room temperature; Solid product is separated, washes with water, vacuum drying, obtain canescence adsorbing material after pulverizing.
The structural characterization of product of the present invention and performance: confirmed structure and the form of adsorption microspheres by scanning electron microscope (SEM), X-ray powder diffraction (XRD), tested the pore structure of adsorption microspheres by BET specific surface area analysis.
From accompanying drawing 1 it can be seen that attapulgite raw ore takes on a red color, for zonal distribution, rich reserves, after hydrothermal treatment consists, obtain canescence adsorbing material.
From accompanying drawing 2 it can be seen that attapulgite is nano bar-shape structure, rod is brilliant in state of aggregation, is associated with lamellar or particulate matter; After PROCESS FOR TREATMENT of the present invention, rhabdolith disappears, and defines the uniform microsphere that surface is porose, and microsphere is formed by substantial amounts of nanoparticle aggregation.
Accompanying drawing 3 can be seen that, attapulgite clay raw ore locates to occur in that respectively the characteristic diffraction peak of (110) and (200) crystal face of attapulgite in 2 θ=8.38 ° and 2 θ=13.85 °, stronger Quartz Characteristics peak is occurred in that at 2 θ=26.68 ° places, the characteristic peak of dolomite is occurred in that at 2 θ=30.09 ° places, illustrate in attapulgite clay raw ore except attapulgite, also have quartz and the assorted ore deposit of dolomite; After the method for the invention processes, attapulgite, quartz and dolomite characteristic peak disappear, and do not have new peak to occur simultaneously, illustrate that under thermal and hydric environment, the restructuring of several materials generates the silicate of low-crystallinity.
From accompanying drawing 4 it 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 it can be seen that the saturated adsorption capacity of chlortetracycline is 376mg/g by adsorption microspheres, 2.31 times of attapulgite clay raw ore (163mg/g) adsorbance are reached; The saturated adsorption capacity of heavy metal copper ion is 280.2mg/g, has reached 2.67 times of attapulgite clay raw ore adsorbance (105.1mg/g); Saturated adsorption capacity to dyestuff methylene blue is 580.6mg/g, has reached 3.27 times of attapulgite clay raw ore adsorbance (177.5mg/g).
From subordinate list 1 it can be seen that after the method for the invention processes, attapulgite clay specific surface area is from the 54.67m of former attapulgite clay2/ g increases to 509.86m2/g。
Table 1
。
Claims (10)
1. utilize the method that red attapulgite stone clay prepares the hybrid mesoporous adsorption microspheres of micro-nano, it is characterised in that: it is after red attapulgite stone clay is mixed with silicate and is fully ground, 80-140 DEG C of microwave heating activation 0.5-4h;Then it is dispersed in aqueous solutions of organic acids by solid-to-liquid ratio 1:9.5, adds aqueous metal salt, be sufficiently stirred for mix homogeneously; The suspension obtained is proceeded in the hydrothermal reaction kettle of tool tetrafluoro liner, temperature 160 ~ 260 DEG C reaction 2 ~ 48h, then it is cooled to room temperature with 10 DEG C/min rate program; Product separating, washing, drying, pulverizing, obtain adsorption microspheres.
2. the method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano according to claim 1, it is characterized in that: described red attapulgite stone clay is attapulgite content is the rich ferrosilicate clay of 10-40%, color and luster is brick-red, containing at least one associated minerals in quartz, dolomite, calcite, montmorillonite and chlorite.
3. the method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano according to claim 1, it is characterised in that: described silicate is the one in sodium silicate, potassium silicate, potassium metasilicate, sodium potassium silicate, just (partially) Lithium metasilicate, orthosilicic acid, metasilicic acid.
4. the method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano according to claim 1, it is characterised in that: described slaine is both magnesium salt and zinc salt compositions; Wherein, magnesium salt is magnesium chloride, magnesium acetate, magnesium nitrate, Diethoxymagnesium, magnesium sulfate, magnesium stearate; Described zinc salt is zinc acetate, zinc chloride, zinc sulfate, zinc nitrate, zinc citrate, zinc oxalate, zinc gluconate; In compositions, zinc salt accounts for the mass fraction of magnesium salt is 1-25%, and metal salt compositions quality is the 10-80% of attapulgite clay mass fraction.
5. the method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano according to claim 1, it is characterised in that: described organic acid is at least one in citric acid, benzoic acid, ethylenediaminetetraacetic acid, oxalic acid, acetic acid, ethanedioic acid, maleic acid, formic acid, glycolic.
6. the method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano according to claim 1, it is characterised in that: the mixture of attapulgite clay and silicate is ground processing, and at 80-140 DEG C of microwave heating activation 0.5-4h.
7. the method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano according to claim 1, it is characterised in that: silicate quality is the 10%-100% of attapulgite clay quality.
8. the method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano according to claim 1, it is characterised in that: the solid-to-liquid ratio of reaction system is 1:9.5.
9. the method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano according to claim 1, it is characterised in that: organic acid addition is the 0.25%-2% of attapulgite clay mass fraction.
10. the method utilizing red attapulgite stone clay to prepare the hybrid mesoporous adsorption microspheres of micro-nano according to claim 1, it is characterised in that: hydrothermal temperature is 160 ~ 260 DEG C, and the response time is 2 ~ 48h, 10 DEG C/min of rate of temperature fall.
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