CN117482930A - Preparation method of attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions, attapulgite adsorbent and application thereof - Google Patents
Preparation method of attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions, attapulgite adsorbent and application thereof Download PDFInfo
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 88
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 88
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 58
- 150000002500 ions Chemical class 0.000 title claims abstract description 44
- 239000003463 adsorbent Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 33
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- 238000001354 calcination Methods 0.000 claims description 4
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
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- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 229940045919 sodium polymetaphosphate Drugs 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229940032158 sodium silicate Drugs 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 5
- 230000005593 dissociations Effects 0.000 abstract description 5
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 7
- 229910052793 cadmium Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
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- 238000009792 diffusion process Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
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- 239000003245 coal Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 238000007789 sealing Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/02—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of water pollution treatment, and particularly relates to a preparation method of an attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions, and a product and application thereof. The preparation method comprises the following steps: carrying out dry-wet integrated purification and dissociation treatment on the APT to obtain refined modified attapulgite; the refined modified attapulgite is calcined at different rates to obtain the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions. According to the invention, the APT is refined and modified, so that the APT has a larger specific surface area and good dispersion capacity, more adsorption sites are exposed as an excellent natural adsorbent, the internal pore canal of the APT is effectively dredged, and the prepared thermally modified refined attapulgite adsorbent can greatly improve the rapid adsorption and selective adsorption capacity of heavy metals, so that an effective solution is provided for the treatment of dangerous and urgent heavy metal pollution.
Description
Technical Field
The invention belongs to the technical field of heavy metal ion adsorption, and particularly relates to a preparation method of an attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions, a product and application thereof.
Background
With the rapid development of modern industry, the environment is more and more polluted than the past, and one of the main pollutants in the environment is heavy metal ions. Heavy metal ions in wastewater are mainly from paint, coal combustion, mining activities, tanneries and battery manufacturing. Since heavy metal ions are not biodegradable in nature, which means that they accumulate in organisms and further endanger human health through the food chain, they must be removed from the wastewater.
Cadmium is an element toxic to the environment, cannot be decomposed into harmless products, and is easily accumulated in the human body. In addition, even at very low doses, elemental cadmium can damage the liver, lungs, and kidneys, causing fractures and destruction of erythrocytes. Over the past several decades, more and more cadmium is released into the environment through industrial waste water, mining operations, and the burning of coal and oil. Cadmium pollution in water is increasingly common, and cadmium becomes a main water pollutant, so that animal, plant and human health is seriously affected.
Lead is fed into the human body through the feeding and inhalation routes of food lead, dust lead and the like in daily diet and workplaces. Lead is very dangerous when absorbed and accumulated in the major organs of the human body, and causes a series of symptoms due to the contact time and the dose. Lead in adults can lead to elevated blood pressure, slow nerve conduction, fatigue, mood swings, somnolence, inattention, fertility disorders, hyposexuality, headache, constipation, severe encephalopathy or death.
Precipitation, ion exchange, solvent extraction, reverse osmosis, etc. are common methods for removing heavy metal ions from aqueous solutions, but these methods are either costly or inefficient. Adsorption is one of a few promising alternatives, and has proven to be one of the most cost-effective and efficient methods for removing heavy metals from wastewater. A variety of adsorbents have been developed, including pectin dust, natural zeolite, biogas slurry residue, chitosan, sporopollen, biological adsorbents, and zeolite MCM-22. Compared with the adsorbents, the Attapulgite (APT) has the advantages of low price, high efficiency and the like due to the inherent physical properties, large surface area, microporous structure, high adsorption capacity, surface reactivity and the like, and plays a key role in immobilization and pollution transfer prevention. In recent years, attapulgite has been used for treating wastewater contaminated with heavy metals.
Disclosure of Invention
The invention aims to provide a preparation method, a product and application of an attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions. The APT is primarily refined and modified, and the impurity minerals are removed to enable the APT to have larger specific surface area and good dispersion capacity, so that the APT is used as an excellent adsorbent or adsorbent carrier, and then the APT is firmly loaded on the surface of the APT through high-temperature calcination treatment, so that the adsorption sites on the surface of the APT are effectively increased, the complexing capacity of the APT is improved, the prepared modified attapulgite adsorbent has extremely high initial adsorption rate on heavy metal, and the removal rate of more than 70% can be achieved in extremely short time (10 s), so that an effective treatment method is provided for solving dangerous and emergent heavy metal pollution accidents.
According to one of the technical schemes, the preparation method of the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions comprises the following steps:
step A: refining and modifying the attapulgite to obtain refined modified attapulgite;
and (B) step (B): and in an air atmosphere, calcining the refined modified attapulgite at different rates to obtain the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions.
Further, the step a specifically includes: placing the attapulgite raw ore powder into a dispersing agent solution, carrying out ultrasonic treatment after strong shearing treatment on micro-areas, standing to remove sediment, and carrying out fractional centrifugation, drying and grinding on the attapulgite slurry to obtain the refined modified attapulgite.
Further, the particle size of the attapulgite raw mineral powder is that the attapulgite raw mineral powder is sieved by a 200-mesh sieve; the mixing mass volume ratio of the attapulgite raw mineral powder and the dispersant solution is 1g to 10mL; shearing rate is 1500-3000 r/min, shearing is carried out for 0.5h, and ultrasonic is carried out for 1h; the drying temperature is 60-105 ℃, and the grinding is carried out by a 200-mesh sieve.
Further, in the step A, the dispersing agent is one or more of sodium polyacrylate, sodium polymetaphosphate, sodium pyrophosphate, sodium silicate and sodium orthophosphate; the mass of the dispersing agent is 1-5% of the mass of the attapulgite raw mineral powder.
Further, in the step A, the fractional centrifugation at least comprises more than two stages of centrifugation treatment, wherein the first stage centrifugation speed is 800-2800 r/min, and the centrifugation time is 30-120 min; the second-stage centrifugal rotating speed is 8000-10000 r/min, and the centrifugal time is 5-30 min.
Further, in the step B, the calcination temperature is 200-1000 ℃, the heating speed is 2-10 ℃/min, and the heat treatment time is 1-3 h.
According to the second technical scheme, the attapulgite adsorbent for quickly adsorbing and removing the heavy metal ions is prepared by the preparation method of the attapulgite adsorbent for quickly adsorbing and removing the heavy metal ions.
According to the third technical scheme, the application of the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions in the treatment of heavy metal polluted wastewater is provided.
Further, the heavy metal in the heavy metal polluted wastewater is one or more of copper ions, lead ions, zinc ions or cadmium ions, wherein the concentration of the copper ions, the zinc ions and the cadmium ions is 10-100 mg/L, and the concentration of the lead ions is 50-200 mg/L; the pH value of the heavy metal polluted wastewater is 3-7.
Compared with the prior art, the invention has the beneficial effects that: the invention prepares the refined modified attapulgite with medium grade or above by a dry-wet integrated purification dissociation method, and prepares the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions by high-temperature calcination treatment, thereby having simple process, no waste acid and waste alkali production, low production cost, easy industrial application and economic and effective new way for emergency treatment of heavy metal polluted wastewater. The obtained attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions has adsorption kinetics of the heavy metal ions conforming to an Elovich model, and the initial adsorption rate reaches 10 4 mg/(g min) is higher than that, and the removal rate of the catalyst is higher than 80% after adsorption for 5 min. The method provides a new economic and effective way for treating the wastewater polluted by heavy metal ions, especially dangerous emergency treatment, and also opens up a new thought for the high-value utilization of low-grade attapulgite.
Drawings
FIG. 1 is an XRD pattern of refined modified APT and CAPT prepared in example 1 of the present invention;
FIG. 2 (a) is a scanning electron microscope image of refined modified APT prepared in example 1 of the present invention;
FIG. 2 (b) is a scanning electron microscope image of CAPT prepared in example 1 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
Example 1
(1) Preparation of refined modified APT
In a 3L beaker, 1500mL of 0.3% sodium polyacrylate solution by mass fraction is added, 150g of APT raw mineral powder which is sieved by a 200-mesh sieve is added, shearing is carried out for 30min by a micro-area strong shearing reactor at a speed of 2500r/min, and ultrasonic treatment is carried out for 1h. Standing for a period of time, discarding the bottom sediment, and carrying out fractional centrifugation on the upper APT slurry. The first-stage centrifugal speed is 1800r/min, the time is 60min, and the bottom impurity minerals are also discarded; and (3) pouring out supernatant after the primary centrifugation is subjected to secondary centrifugation at 10000r/min for 30min, drying the lower-layer sediment in a baking oven at 60-105 ℃, grinding and sieving with a 200-mesh sieve to finally obtain refined modified APT, and storing in a sealing manner for standby.
SEM analysis is carried out on APT prepared by dry-wet integrated purification and dissociation of APT raw ore powder, and the raw ore contains a large amount of bulk impurity minerals, APT rod-shaped crystals are scattered in the raw ore in a disordered way, and the APT rod-shaped crystals are in a rod crystal aggregate or rod crystal bundle form and have less rod crystal exposure; after dry-wet integrated purification and dissociation, the agglomeration bonding phenomenon on APT is obviously improved, rod crystals and rod crystal bundles are obviously increased, bulk impurities are obviously reduced, the rod crystal dispersion degree is obviously improved, and the specific surface area is increased. The main constituent element of the APT was O, si, mg, al, fe, K, ca by XRF elemental analysis. After dry-wet integrated purification and dissociation, the mass fraction of MgO is increased from 5.64% to 7.24%, al 2 O 3 The mass fraction of Fe is reduced from 14.69% to 14.85% 2 O 3 The mass fraction of CaO is reduced from 16.63% to 14.85%, the mass fraction of CaO is reduced from 4.47% to 0.73%, and most of impurities are removed. The main element types of the APT are not changed obviously after pretreatment, which indicates that the structure of the APT is not changed, and XRD analysis (shown in figure 1) also proves that a large amount of quartz and calcite are removed, and only the content of dolomite is not changed greatly.
(2) Preparation of CAPT
And (2) placing 2g of the boat-shaped corundum containing the refined and modified APT prepared in the step (1) into a muffle furnace, setting the heating rate to be 5 ℃/min, respectively setting the heat treatment temperature to be 300, 400, 500 and 600 ℃, carrying out heat treatment for 2 hours, and sealing and storing the corundum for later use when the reaction temperature is reduced to room temperature, namely the CAPT, namely the adsorbent required for removing heavy metal ions in the water body in the embodiment.
FIG. 1 shows XRD patterns of refined and modified APT and CAPT prepared in this example, from which it can be seen that APT has been subjected to high temperature thermal modificationThe intensity of the characteristic diffraction peak is obviously reduced, which indicates that the crystal structure of APT is changed, part of zeolite water and structural water are lost, and the pore channel is further opened.
FIG. 2 (a) is a scanning electron microscope image of refined and modified APT prepared in example 1 of the present invention, and FIG. 2 (b) is a scanning electron microscope image of CAPT prepared in example 1 of the present invention. As can be seen from the figure, the prepared refined modified APT has high dispersion degree of the rod crystal and large length-diameter ratio, and is an excellent natural one-dimensional adsorbent; the CAPT after the high-temperature heat modification treatment has the advantages that the length-diameter ratio is reduced, the aggregation phenomenon exists in the rod crystal, but the specific surface area of the adsorbent is increased through the dredged pore canal, meanwhile, the electronegativity of the surface of the adsorbent is enhanced, and the adsorption of cations is facilitated.
(3) Effect verification
(1) Preparing an experimental solution: weigh 3.840g Cu (NO) 3 ) 2 ·3H 2 O、4.596g Zn(NO 3 ) 2 ·6H 2 O、2.052g CdCl 2 ·2.5H 2 O、1.615g Pb(NO 3 ) 2 Respectively dissolving in a proper amount of deionized water, transferring to a 1000mL volumetric flask, continuously using deionized water to fix the volume, preparing copper, zinc, cadmium and lead stock solutions with the concentration of 1000mg/L, and further diluting into copper, zinc, cadmium and lead solutions with the specific concentrations of 100mg/L, 200mg/L, 300mg/L, 400mg/L and 500 mg/L.
(2) 6 conical flasks of 100mL were taken and 20mL of Cd having a pH of 6.5 and a concentration of 100mg/L were added, respectively 2+ The solution was added with 5g/L of APT raw ore powder, refined modified APT, CAPT-3 (heat treatment temperature 300 ℃), CAPT-4 (heat treatment temperature 400 ℃), CAPT-5 (heat treatment temperature 500 ℃) and CAPT-6 (heat treatment temperature 600 ℃) in this order, and water was applied at a rate of 120r/min at 30℃in a water bathMiddle oscillating for 24h, taking Cd at regular intervals 2+ The solution was then filtered through a 0.45 μm microporous filter membrane and the Cd content of the solution was determined by the ICP-AES method 2+ Is a concentration of (3).
(2) The results show that: APT crude ore vs Cd 2+ The removal rate of the catalyst is 36.5 percent, and the Cd is subjected to APT after refining and modification treatment 2+ The removal rate of the catalyst is slightly improved to 62.1 percent, because a large amount of quartz, calcite and other impurity minerals are removed in the refining and modification process, meanwhile, the rod crystal aggregates are more dissociated, the specific surface area of the APT is improved due to the increase of the rod crystal bundles and the rod crystal proportion, more pore channels are exposed, and the contact area of adsorption sites is increased. CAPT is relative to APT crude ore or refined modified APT to Cd 2+ The adsorption performance of (C) is obviously improved, wherein CAPT-4 is used for Cd 2+ The adsorption performance of (C) is best, and the removal rate reaches 97.6% which is higher than 79.6% of CAPT-3, 88.6% of CAPT-5 and 80.6% of CAPT-6. Thus, (3) and (4) experiments were performed on the CAPT-4 basis.
(3) Taking 4 conical flasks of 100mL, adding 20mL of Cd with pH of 6.5 and concentration of 100mg/L respectively 2+ Solution, cu with pH of 4.9 and concentration of 100mg/L 2+ Pb in solution with pH 4.7 and concentration of 100mg/L 2+ Solution and Zn with pH 5.6 and concentration of 100mg/L 2+ And sequentially adding CAPT-4 into the solution according to the adding amount of 5g/L, oscillating for 24 hours in a water bath at the temperature of 30 ℃ at the speed of 120r/min, taking the heavy metal ion solution at regular intervals, passing through a 0.45 mu m microporous filter membrane, and respectively measuring the concentration of the heavy metal ions in the solution by an ICP-AES method.
(3) The results show that: CAPT-4 pair Cd in solution 2+ 、Cu 2+ 、Pb 2+ And Zn 2+ The adsorption process of (a) can be roughly divided into three stages: a rapid adsorption stage (0-1 h), a slow adsorption stage (1-24 h) and an adsorption equilibrium stage (after 24 h). The nonlinear dynamics model fitting result shows that CAPT-4 is used for solving Cd in the solution 2+ 、Cu 2+ 、Pb 2+ And Zn 2+ The adsorption process of (2) well accords with an Elovich model, and the correlation coefficient R thereof 2 0.9996, 0.9985, 0.9983 and 0.9979 are respectively achieved, which are far higher than 0.9545, 0.9093, 0.8352 and 0.8928 of pseudo-second order kinetics, and 0.9298, 0.8607 of pseudo-first order kinetics,0.7299 and 0.8349. And more importantly, CAPT-4 pairs of Cd in solution 2+ 、Cu 2+ 、Pb 2+ And Zn 2+ Respectively reaches 1.621×10 13 mg·g -1 ·min、8.916*10 5 mg·g -1 ·min、2.38*10 44 mg·g -1 Min and 4.273 x 10 4 mg·g -1 Min, wherein CAPT-4 is specific to Pb in the solution 2+ The initial adsorption rate of (2) is highest, reaching surprisingly 2.38 x 10 44 mg·g -1 Min, and the maximum adsorption amount reaches 84.43 mg.g -1 . This means that when lead-containing heavy metal sewage is treated in an emergency, the Pb can be removed instantaneously (10 s) by adding a sufficient amount of CAPT-4 2+ Is a target of (a). The method provides an excellent option for emergency treatment of heavy metal sewage, and has important practical significance. The fit result of the intra-particle diffusion model shows that CAPT-4 pairs Cd in the solution 2+ 、Cu 2+ 、Pb 2+ And Zn 2+ The adsorption process of (2) is mainly controlled by the steps of membrane diffusion and intra-particle diffusion.
(4) 1 of a 100mL Erlenmeyer flask was taken and 20mL of Cd was added 2+ 、Cu 2+ 、Pb 2+ And Zn 2+ CAPT-4 was added in an amount of 5g/L, and the mixture was shaken in a water bath at a rate of 120r/min at 30℃for 24 hours, and the mixture was taken at regular intervals and passed through a 0.45 μm microporous filter membrane, and the concentration of heavy metal ions in the solution was measured by the ICP-AES method.
(4) The results show that: CAPT-4 pair of Cd in mixed heavy metal ion solution 2+ 、Cu 2+ 、Pb 2+ And Zn 2+ The adsorption process is similar to the adsorption process of a single heavy metal ion solution, and compared with the primary kinetic process, the mixed adsorption process is more in line with the secondary kinetic process. More importantly, the Elovich model is a best-fit dynamic model. This shows that CAPT-4 adsorption of mixed heavy metal ion solution still accords with the characteristic of rapid adsorption, but the initial adsorption rate is slightly reduced to 1.890 x 10 respectively 4 mg·g -1 ·min、2.573*10 2 mg·g -1 ·min、2.758*10 5 mg·g -1 Min sum9.731*10 3 mg·g -1 Min, and CAPT-4 pair mix Cd in heavy metal ion solution 2+ 、Cu 2+ 、Pb 2+ And Zn 2+ The removal rates of (a) were 20.6%, 51.1%, 92.72% and 22.8%, respectively. Thus, CAPT-4 pair mixes Cd in heavy metal ion solution 2+ 、Cu 2+ 、Pb 2+ And Zn 2+ The adsorption process of (2) has selectivity, and CAPT-4 is used for adsorbing Pb in the mixed solution under the same conditions 2+ The adsorption capacity of (C) is maximum and reaches 15.66 mg.g -1 The removal efficiency is highest.
In the description herein, reference to the terms "embodiment," "example," "specific example," and the like, means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (9)
1. The preparation method of the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions is characterized by comprising the following steps of:
step A: refining and modifying the attapulgite to obtain refined modified attapulgite;
and (B) step (B): and in the air atmosphere, calcining the refined modified attapulgite to obtain the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions.
2. The method for preparing the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions according to claim 1, wherein the step a specifically comprises: placing the attapulgite raw ore powder into a dispersing agent solution, carrying out ultrasonic treatment after strong shearing treatment on the micro-areas, standing to remove sediment, and carrying out fractional centrifugation, drying and grinding on the attapulgite slurry to obtain the modified attapulgite.
3. The method for preparing the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions according to claim 2, wherein the particle size of the raw attapulgite mineral powder is 200 mesh; the mixing mass volume ratio of the attapulgite raw mineral powder and the dispersant solution is 1g to 10mL; shearing rate is 1500-3000 r/min, shearing is carried out for 0.5h, and ultrasonic is carried out for 1h; the drying temperature is 60-105 ℃, and the grinding is carried out by a 200-mesh sieve.
4. The method for preparing the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions according to claim 2, wherein in the step A, the dispersing agent is one or more of sodium polyacrylate, sodium polymetaphosphate, sodium pyrophosphate, sodium silicate and sodium orthophosphate; the mass of the dispersing agent is 1-5% of the mass of the attapulgite raw mineral powder.
5. The method for preparing the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions according to claim 2, wherein in the step A, the fractional centrifugation at least comprises more than two stages of centrifugation treatment, wherein the first stage centrifugation speed is 800-2800 r/min, and the centrifugation time is 30-120 min; the second-stage centrifugal rotating speed is 8000-10000 r/min, and the centrifugal time is 5-30 min.
6. The method for preparing the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions according to claim 1, wherein in the step B, the calcining temperature is 200-1000 ℃, the heating rate is 2-10 ℃/min, and the heat treatment time is 1-3 h.
7. An attapulgite adsorbent for rapid adsorption removal of heavy metal ions prepared by the method for preparing an attapulgite adsorbent for rapid adsorption removal of heavy metal ions according to any one of claims 1 to 6.
8. Use of the attapulgite adsorbent for rapidly adsorbing and removing heavy metal ions according to claim 7 in heavy metal sewage treatment.
9. The application of the attapulgite adsorbent for quickly absorbing and removing heavy metal ions in heavy metal sewage treatment according to claim 8, wherein the heavy metal in the heavy metal polluted wastewater is one or more of copper ions, lead ions, zinc ions and cadmium ions, the concentration of the copper, zinc and cadmium ions is 10-100 mg/L, and the concentration of the lead ions is 50-200 mg/L;
the pH value of the heavy metal polluted wastewater is 3-7.
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