CN113041991A - Preparation method and application of lanthanum-loaded attapulgite phosphorus removal adsorbent - Google Patents
Preparation method and application of lanthanum-loaded attapulgite phosphorus removal adsorbent Download PDFInfo
- Publication number
- CN113041991A CN113041991A CN202110252297.0A CN202110252297A CN113041991A CN 113041991 A CN113041991 A CN 113041991A CN 202110252297 A CN202110252297 A CN 202110252297A CN 113041991 A CN113041991 A CN 113041991A
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- solution
- lanthanum
- pal
- loaded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 119
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 117
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 69
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003463 adsorbent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000011574 phosphorus Substances 0.000 title claims abstract description 27
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 80
- 239000002131 composite material Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 39
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 29
- 239000010452 phosphate Substances 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000002244 precipitate Substances 0.000 claims description 18
- 230000009471 action Effects 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- 230000002860 competitive effect Effects 0.000 claims description 4
- 229910020854 La(OH)3 Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000036619 pore blockages Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 10
- 239000011707 mineral Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 6
- 229940010698 activated attapulgite Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 239000000391 magnesium silicate Substances 0.000 description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 description 3
- 235000019792 magnesium silicate Nutrition 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- -1 lanthanum phosphate compound Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 229910001464 rare earth metal phosphate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- 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
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
Abstract
The invention relates to a preparation method of a phosphorus removal adsorbent for lanthanum-loaded attapulgite, which comprises the following steps: s1, roasting the attapulgite material to obtain the attapulgite heat activated material PAL-H. S2, adding alkali liquor into the soluble lanthanum salt solution, adjusting the pH value, and carrying out ultrasonic treatment to obtain La (OH)3The solution is loaded. S3, adding the PAL-H of the attapulgite heat activated material obtained in the step S1 into the La (OH) obtained in the step S23And reacting in the load solution to obtain the lanthanum-loaded attapulgite composite PAL-La. The adsorbent prepared by the preparation method can provide abundant binding sites, has excellent adsorption capacity on phosphate and does not cause the problem of pore blockage of the adsorbent。
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method and application of a lanthanum-loaded attapulgite phosphorus removal adsorbent.
Background
Excessive phosphorus (P) causes eutrophication of lakes and rivers, which leads to dangerous algae outbreaks, dissolved oxygen depletion and fish death, seriously disturbs the ecological balance of organisms in the water body, and damages public health. Therefore, there is a need for viable technologies to inhibit phosphorus from entering natural water bodies. In the prior art, the water body phosphorus removal technology mainly comprises a chemical precipitation technology, a biological treatment technology, a membrane treatment technology and an adsorption technology. Wherein, the chemical precipitation dephosphorization technique is mostly suitable for the preliminary treatment of the high-concentration phosphorus-containing wastewater, and other techniques are needed to further reduce the phosphate in the water. In the actual operation process of the biological method, the operation conditions are required to be strictly controlled, and the proportion of other nutrient elements is required to be regulated and controlled to ensure the stable performance of the phosphorus absorption function of the activated sludge microorganisms, so the operation, maintenance and management of the biological method are complicated. In the membrane bioreactor technology which has gained much attention in recent years, the membrane module faces serious membrane pollution problem, and the cost for cleaning and replacing the membrane module greatly increases the cost for treating the phosphorus-containing wastewater by applying the membrane technology. Compared with other phosphorus removal technologies, the adsorption technology has outstanding advantages. The efficient, nontoxic and renewable adsorbent is the core of the application and development of the adsorption phosphorus removal technology, but the phosphorus removal efficiency of the traditional adsorbent material is difficult to fully meet the increasingly strict water treatment discharge standard at present in the light of the higher water environment protection requirement at present, so that the research and development of a novel efficient phosphorus removal adsorbent material have important significance.
In the development of an adsorbent for effectively enhancing phosphorus removal, natural mineral materials are becoming hot spots of current research on adsorption materials due to low price, easy availability and unique porous structure. Many natural minerals are positively charged on their surfaces and can electrostatically adsorb negatively charged anions in water. In addition, the minerals contain abundant metal minerals (such as calcium, magnesium, aluminum oxides, etc.) which can generate inner layer complexation reaction with phosphate. However, since minerals are formed in natural environments and have less active adsorption groups due to environmental factors and geological conditions of surrounding production sites, physical or chemical modification is required to improve the adsorption efficiency of mineral materials to target anions.
Attapulgite, also known as palygorskite, is a water-bearing stratum chain magnesium silicate mineral, the crystal microstructure of which is needle-shaped, fibrous or fibrous aggregate, is a dominant mineral resource in China, and has great development and utilization values. The attapulgite rock stratum has low hardness, shallow buried depth, convenient exploitation and lower requirement on processing equipment. The attapulgite has lower price than other mineral materials by comprehensively considering the mining cost, so the attapulgite has obvious price competitiveness and market application value. The attapulgite has a unique nano-rod crystal structure, so that the attapulgite has high specific surface area and porosity. In addition, the crystal structure of the attapulgite is often doped with a certain amount of metal components such as calcium, magnesium and the like according to different geological conditions of a producing area besides metal elements such as magnesium and aluminum, so that the attapulgite has the potential of forming surface precipitates with phosphate in water.
In addition, phosphate can form stable inner layer complex with a plurality of metal ions through ligand exchange, so that metal oxide loading is a phosphorus removal adsorbent modification method with wide application. Lanthanum oxide is widely used for preparing the sewage dephosphorization adsorbent because lanthanum has excellent affinity with phosphate in water. The lanthanum phosphate compound is the most insoluble compound in rare earth metal phosphate in the natural world at present, the solubility of lanthanum phosphate is further reduced along with the increase of the temperature of the solution, and the lanthanum phosphate compound still keeps a stable precipitate form under the high-temperature condition and is not easy to dissolve. The treatment effect of lanthanum on phosphate in water is obviously better than that of metal aluminum salt and iron salt commonly used for water treatment, and more importantly, lanthanum has good biological safety and can fully ensure that the lanthanum has no health risk when being applied in the field of water treatment.
Disclosure of Invention
Technical problem to be solved
In order to solve the bottleneck problems of few active adsorption sites and low pollutant adsorption capacity of the mineral material phosphorus removal adsorbent in the prior art, the invention provides a preparation method of the lanthanum-loaded attapulgite phosphorus removal adsorbent. In order to solve the technical problems, the invention also provides application of the lanthanum-loaded attapulgite phosphorus removal adsorbent.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a preparation method of the attapulgite phosphorus removal adsorbent loaded with lanthanum comprises the following steps:
s1, pretreatment of the attapulgite material: roasting the attapulgite material to obtain an attapulgite heat-activated material PAL-H;
S2、La(OH)3preparing a loading solution: adding alkali liquor into soluble lanthanum salt solution, adjusting pH, and performing ultrasonic treatment to obtain La (OH)3Loading the solution;
s3, adding the PAL-H of the attapulgite heat activated material obtained in the step S1 into the La (OH) obtained in the step S23And reacting in the load solution to obtain the lanthanum-loaded attapulgite composite PAL-La.
In the preparation method, in step S1, the attapulgite is preferably roasted at 700-800 ℃ for 4-8 hours.
The preparation method as described above, preferably, in step S2, La (NO) is adjusted with NaOH solution3)3The pH value of the solution is then placed in an ultrasonic cell disruptor for ultrasonic treatment for 10-30 min to obtain La (OH)3The solution is loaded.
The preparation method as described above, preferably, in step S3, adding the attapulgite heat-activated material PAL-H into La (OH)3After the solution is loaded, carrying out reaction under the action of ultrasound, and then carrying out reaction under the condition of water bath to obtain a turbid solution;
after the reaction is finished, centrifuging the turbid solution, washing and filtering the precipitate;
drying and grinding the filtered precipitate to obtain the lanthanum-loaded attapulgite composite PAL-La.
In the preparation method as described above, preferably, in step S2, La (NO) is adjusted with NaOH or KOH solution3)3The pH value of the solution;
the concentration of the NaOH or KOH solution is 1 mol/L;
the La (NO)3)3The concentration of the solution is 0.1 mol/L;
the La (NO)3)3The pH of the solution was adjusted to 10.
The preparation method as described above, preferably, in step S3, the attapulgite heat activated material PAL-H and La (OH)3The mass ratio of (1): 1-1: 1.6.
in the preparation method, preferably, in step S3, the reaction time under the action of ultrasound is 10-30 min, and the reaction time under the water bath condition is 5-10 h;
the temperature of the water bath is 60-70 ℃.
In the preparation method, preferably, in step S3, the precipitate is dried at 60-80 ℃ for 12-48 h;
grinding the precipitate, and sieving with 200 mesh sieve to obtain the lanthanum-loaded attapulgite composite PAL-La.
The invention also provides an application of the lanthanum-loaded attapulgite composite PAL-La prepared by the preparation method, wherein the lanthanum-loaded attapulgite composite PAL-La is used for adsorbing phosphate;
the adsorption rate of the lanthanum attapulgite composite PAL-La on a solution with the phosphate concentration below 50mg/L and the pH range of 3-11 is more than or equal to 99%.
The use as described above, preferably, the lanthanum attapulgite composite PAL-La is used to adsorb phosphate in a competitive anion environment;
the competing anion comprises SO4 2-、NO3 -、HCO3 -And Cl-。
(III) advantageous effects
The invention has the beneficial effects that:
the PAL-La adsorbent of the lanthanum-loaded attapulgite composite material prepared by the preparation method can provide abundant binding sites, and can not cause the problem of pore blockage of the adsorbent.
The lanthanum-loaded attapulgite composite PAL-La prepared by the preparation method has excellent phosphate adsorption capacity, can almost realize complete phosphate separation for a solution with the phosphate concentration below 50mg/L and the pH range of 3-11, and has the phosphate residual concentration not more than 0.5 mg/L. The existence of high concentration competitive anions such as sulfate, nitrate, bicarbonate and chloride with the concentration ranging from 5 to 50mg/L does not have significant influence on the adsorption effect of the PAL-La adsorbent of the lanthanum-loaded attapulgite composite material.
In addition, the PAL-La adsorbent has strong recoverability, good settleability and high stability, and the leaching of lanthanum can be ignored even under the ultrasonic condition. PAL-La shows great advantages in the adsorption capacity and the usage amount of lanthanum, and has good application prospect as an economic and effective adsorbent.
Drawings
FIG. 1 is a scanning electron microscope image of the attapulgite lanthanum-loaded composite material in the invention;
FIG. 1a is a scanning electron microscope image of the natural attapulgite (PAL) of the present invention;
FIG. 1b is a scanning electron microscope image of the calcined attapulgite (PAL-H) in the present invention;
FIG. 1c is a scanning electron microscope image of lanthanum-loaded attapulgite (PAL-La) according to the present invention;
FIG. 2 shows attapulgite, quartz, dolomite, calcium/magnesium silicate and La (OH) according to the present invention3X-ray diffraction diagram (in the figure, the symbol o represents attapulgite, quartz, ● dolomite, Δ calcium/magnesium silicate, ■ La (OH)3)；
FIG. 3 is a graph showing the influence of roasting time and temperature on the adsorption performance of natural attapulgite phosphate in the present invention;
FIG. 4 is a phosphate adsorption isotherm of the lanthanum-loaded composite material on the surface of the attapulgite and a curve fitted by a Langmuir, Freundlich model.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The embodiment of the invention provides a preparation method of a phosphorus removal adsorbent for lanthanum-loaded attapulgite, which comprises the following steps:
s1, pretreatment of the attapulgite material: roasting the attapulgite at the temperature of 700-800 ℃ for 4-5 hours to obtain the attapulgite heat-activated material PAL-H.
S2, lanthanum ion pretreatment: regulating La (NO) with NaOH solution3)3The pH value of the solution is then placed in an ultrasonic cell disruptor for ultrasonic treatment for 10-30 min to obtain La (OH)3The solution is loaded.
S3, adding the attapulgite heat activated material PAL-H into La (OH)3After the solution is loaded, the reaction is carried out under the action of ultrasound, and then the reaction is carried out under the condition of water bath, so as to obtain turbid liquid. After the reaction is finished, the turbid solution is centrifuged, and the precipitate is washed and filtered. Drying and grinding the filtered precipitate to obtain the lanthanum-loaded attapulgite composite PAL-La.
In the embodiment of the invention, the fiber cross-linked structure of the attapulgite provides sufficient loading sites for lanthanum hydroxide nanoparticles, the lanthanum hydroxide nanoparticles can be uniformly distributed on the surface of the attapulgite under the ultrasonic action, and the prepared lanthanum-loaded attapulgite composite PAL-La adsorbent can provide abundant binding sites and cannot cause the problem of pore blockage of the adsorbent.
The lanthanum-loaded attapulgite composite PAL-La prepared by the preparation method has excellent phosphate adsorption capacity, can almost realize complete phosphate separation for a solution with the phosphate concentration below 50mg/L and the pH range of 3-11, and has the phosphate residual concentration not more than 0.5 mg/L. The existence of high concentration competitive anions such as sulfate, nitrate, bicarbonate and chloride with the concentration ranging from 5 to 50mg/L does not have significant influence on the adsorption effect of the PAL-La adsorbent of the lanthanum-loaded attapulgite composite material. In addition, the PAL-La adsorbent has strong recoverability, good settleability and high stability, and the leaching of lanthanum can be ignored even under the ultrasonic condition. PAL-La shows great advantages in the adsorption capacity and the usage amount of lanthanum, and has good application prospect as an economic and effective adsorbent.
Preferably, in step S2, La (NO) is adjusted by NaOH or KOH solution3)3The pH value of the solution;
the concentration of the NaOH or KOH solution is 1 mol/L;
the La (NO)3)3The concentration of the solution is 0.1 mol/L;
the La (NO)3)3The pH of the solution was adjusted to 10. In the examples of the present invention, La (NO) was used for the synthesis of lanthanum hydroxide3)3And the concentration of NaOH or KOH are also key parameters, La (NO)3)3And too high concentration of NaOH or KOH will block the cross-linked pores of the attapulgite, while too low concentration will not exert higher phosphorus adsorption efficiency due to less lanthanum loading. The concentration of NaOH or KOH solution is 1mol/L, La (NO)3)3The concentration of the solution is 0.1mol/L, which is the optimal preparation concentration.
Preferably, in step S3, the attapulgite heat activated material PAL-H and La (OH)3The mass ratio of (1): 1-1: 1.6.
preferably, in the step S3, the reaction time under the ultrasonic action is 10-30 min, the reaction time under the water bath condition is 5-10h, and the water bath temperature is 60-70 ℃.
Preferably, in step S3, the precipitate is dried at 60-65 ℃ for 12-48 h. Grinding the precipitate, and sieving with 200 mesh sieve to obtain the lanthanum-loaded attapulgite composite PAL-La.
Example 1
The embodiment of the invention provides a preparation method of a phosphorus removal adsorbent for lanthanum-loaded attapulgite, and the lanthanum-loaded attapulgite composite material in the embodiment is prepared by adding La (OH) into an attapulgite sample PAL-H3Is prepared in solution. The mass of PAL-H in the lanthanum-loaded attapulgite composite material is 1g, and the specific preparation method comprises the following steps:
s1, pretreatment of the attapulgite material: roasting 1.00g of natural attapulgite material at 500 ℃ for 2H to obtain the attapulgite heat-activated material PAL-H.
S2、La(OH)3Preparation of a loading solution: 50mL of 0.1mol/L La (NO)3)3The solution is placed at a constant temperatureOn the magnetic stirrer, the rotational speed of the magnetic stirrer was set to 120rpm, and 1mol/L NaOH solution was added dropwise until the reaction solution reached a pH of 10. Immediately thereafter, the reaction solution was placed in an ultrasonic cell disruptor and subjected to ultrasonic action at 130W intensity for 10min to sufficiently disperse the reactants to obtain La (OH)3The solution is loaded.
S3, adding PAL-H of the calcined and activated attapulgite sample 1g obtained in the step S1 into La (OH) obtained in the step S23In the load solution, the reaction is carried out for 10min under the action of 130W ultrasound, and then the reaction is carried out for 6h in a water bath kettle at the temperature of 60 ℃. After the reaction solution was subsequently centrifuged at 4000rpm for 10min, the supernatant was decanted off, and the precipitate was washed with deionized water until the pH of the mixed solution became neutral. Drying the filtered solid at 60 ℃ for 48h, grinding the solid by using a mortar to be crushed, and sieving the crushed solid by using a 200-mesh sieve to obtain powder particles, namely the lanthanum-loaded attapulgite composite material which is named PAL-La (500).
Example 2
The embodiment of the invention provides a preparation method of a phosphorus removal adsorbent for lanthanum-loaded attapulgite, and the lanthanum-loaded attapulgite composite material in the embodiment is prepared by adding La (OH) into an attapulgite sample PAL-H3Is prepared in solution. The mass of PAL-H in the lanthanum-loaded attapulgite composite material is 1g, and the specific preparation method comprises the following steps:
s1, pretreatment of the attapulgite material: roasting 1.00g of natural attapulgite material at 600 ℃ for 3H to obtain the attapulgite heat-activated material PAL-H.
S2, lanthanum ion pretreatment: 50mL of 0.1mol/L La (NO)3)3The solution was placed on a constant temperature magnetic stirrer, the rotational speed of the magnetic stirrer was set to 120rpm, and 1mol/L NaOH solution was added dropwise until the pH of the reaction solution reached 10. Immediately thereafter, the reaction solution was placed in an ultrasonic cell disruptor and subjected to ultrasonic action at 130W intensity for 5min to sufficiently disperse the reactants to obtain La (OH)3The solution is loaded.
S3, adding PAL-H of the calcined and activated attapulgite sample 1g obtained in the step S1 into La (OH) obtained in the step S23Reacting in the load solution under the action of 130W ultrasound for 10min, and then in a water bath kettle at 60 DEG CAnd reacting for 6 h. After the reaction solution was subsequently centrifuged at 4000rpm for 10min, the supernatant was decanted off, and the precipitate was washed with deionized water until the pH of the mixed solution became neutral. Drying the filtered solid at 60 ℃ for 48h, grinding the solid by using a mortar to be crushed, and sieving the crushed solid by using a 200-mesh sieve to obtain powder particles, namely the lanthanum-loaded attapulgite composite material which is named PAL-La (600).
Example 3
The embodiment of the invention provides a preparation method of a phosphorus removal adsorbent for lanthanum-loaded attapulgite, and the lanthanum-loaded attapulgite composite material in the embodiment is prepared by adding La (OH) into an attapulgite sample PAL-H3Is prepared in solution. The mass of PAL-H in the lanthanum-loaded attapulgite composite material is 1g, La (OH)3The mass of (2) is 0.95g, and the specific preparation method comprises the following steps:
s1, pretreatment of the attapulgite material: roasting 1.00g of natural attapulgite material at 700 ℃ for 2H to obtain the attapulgite heat-activated material PAL-H.
S2, lanthanum ion pretreatment: 50mL of 0.1mol/L La (NO)3)3The solution was placed on a constant temperature magnetic stirrer, the rotational speed of the magnetic stirrer was set to 120rpm, and 1mol/L NaOH solution was added dropwise until the pH of the reaction solution reached 10. Immediately thereafter, the reaction solution was placed in an ultrasonic cell disruptor and subjected to ultrasonic action at 130W intensity for 10min to sufficiently disperse the reactants to obtain La (OH)3The solution is loaded.
S3, adding PAL-H of the calcined and activated attapulgite sample 1g obtained in the step S1 into La (OH) obtained in the step S23In the load solution, the reaction is carried out for 10min under the action of 130W ultrasound, and then the reaction is carried out for 6h in a water bath kettle at the temperature of 60 ℃. After the reaction solution was subsequently centrifuged at 4000rpm for 10min, the supernatant was decanted off, and the precipitate was washed with deionized water until the pH of the mixed solution became neutral. Drying the filtered solid at 60 ℃ for 48h, grinding the solid by using a mortar to be crushed, and sieving the crushed solid by using a 200-mesh sieve to obtain powder particles, namely the lanthanum-loaded attapulgite composite material which is named PAL-La (700).
Example 4
The embodiment of the invention provides a preparation method of a phosphorus removal adsorbent of lanthanum-loaded attapulgite,the lanthanum-loaded attapulgite composite material in the embodiment is prepared by adding La (OH) into an attapulgite sample PAL-H3Is prepared in solution. The mass of PAL-H in the lanthanum-loaded attapulgite composite material is 1g, and the specific preparation method comprises the following steps:
s1, pretreatment of the attapulgite material: roasting 1.00g of natural attapulgite material at 800 ℃ for 3H to obtain the attapulgite heat-activated material PAL-H.
S2, lanthanum ion pretreatment: 50mL of 0.1mol/L La (NO)3)3The solution was placed on a constant temperature magnetic stirrer, the rotational speed of the magnetic stirrer was set to 120rpm, and 1mol/L NaOH solution was added dropwise until the pH of the reaction solution reached 10. Immediately thereafter, the reaction solution was placed in an ultrasonic cell disruptor and subjected to ultrasonic action at 130W intensity for 10min to sufficiently disperse the reactants to obtain La (OH)3The solution is loaded.
S3, adding PAL-H of the calcined and activated attapulgite sample 1g obtained in the step S1 into La (OH) obtained in the step S23In the load solution, the reaction is carried out for 10min under the action of 130W ultrasound, and then the reaction is carried out for 6h in a water bath kettle at the temperature of 60 ℃. After the reaction solution was subsequently centrifuged at 4000rpm for 10min, the supernatant was decanted off, and the precipitate was washed with deionized water until the pH of the mixed solution became neutral. Drying the filtered solid at 60 ℃ for 48h, grinding the solid by using a mortar to be crushed, and sieving the crushed solid by using a 200-mesh sieve to obtain powder particles, namely the lanthanum-loaded attapulgite composite material which is named PAL-La (800).
The micro-topography of the natural attapulgite (PAL) in the embodiment 3 of the invention, the attapulgite (PAL-H) roasted at the high temperature of 700 ℃ for 4H and the lanthanum-loaded composite material (PAL-La) on the surface of the attapulgite is shown in figure 1.
XRD diffraction patterns of the natural attapulgite (PAL) in the embodiment 3 of the invention, the attapulgite (PAL-H) roasted at the high temperature of 700 ℃ for 4H and the lanthanum-loaded composite material (PAL-La) on the surface of the attapulgite are shown in figure 2.
The attapulgite lanthanum-loaded composite material (PAL-La) prepared in the examples 1 to 4 is used for phosphate adsorption, and the influence of the roasting temperature and the holding time on the phosphate adsorption capacity of the original palygorskite shown in figure 3 is obtained, so that the phosphate adsorption effect of the attapulgite lanthanum-loaded composite material (PAL-La) prepared by roasting attapulgite at the high temperature of 700 ℃ for 4 hours as a raw material is the best, and the example 3 is the best example.
The attapulgite lanthanum-loaded composite material (PAL-La) prepared in the embodiment 3 of the invention, natural attapulgite (PAL) and heat-activated attapulgite (PAL-H) are simultaneously applied to phosphate adsorption, and a phosphate adsorption isotherm comparison graph shown in figure 4 is obtained. Analysis shows that the phosphate removal rate of the adsorbent, namely the attapulgite lanthanum-loaded composite material (PAL-La) is obviously improved compared with other materials by adopting the adsorbent provided by the embodiment of the invention.
The above embodiments are merely illustrative, and not restrictive, of the scope of the invention, and those skilled in the art will be able to make various changes and modifications within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A preparation method of the phosphorus removal adsorbent for the lanthanum-loaded attapulgite is characterized by comprising the following steps:
s1, pretreatment of the attapulgite material: roasting the attapulgite material to obtain an attapulgite heat-activated material PAL-H;
S2、La(OH)3preparing a loading solution: adding alkali liquor into soluble lanthanum salt solution, adjusting pH, and performing ultrasonic treatment to obtain La (OH)3Loading the solution;
s3, adding the PAL-H of the attapulgite heat activated material obtained in the step S1 into the La (OH) obtained in the step S23And reacting in the load solution to obtain the lanthanum-loaded attapulgite composite PAL-La.
2. The preparation method according to claim 1, wherein in step S1, the attapulgite is calcined at a temperature of 700-800 ℃ for 4-8 hours.
3. The method of claim 1, wherein in step S2, La (NO) is adjusted with NaOH solution3)3The pH value of the solution is then put into an ultrasonic cell disruptor for ultrasonic treatment for 10-30 min, obtaining La (OH)3The solution is loaded.
4. The method of claim 1, wherein in step S3, the attapulgite heat activated material PAL-H is added to La (OH)3After the solution is loaded, carrying out reaction under the action of ultrasound, and then carrying out reaction under the condition of water bath to obtain a turbid solution;
after the reaction is finished, centrifuging the turbid solution, washing and filtering the precipitate;
drying and grinding the filtered precipitate to obtain the lanthanum-loaded attapulgite composite PAL-La.
5. The method of claim 1, wherein in step S2, La (NO) is adjusted with NaOH or KOH solution3)3The pH value of the solution;
the concentration of the NaOH or KOH solution is 1 mol/L;
the La (NO)3)3The concentration of the solution is 0.1 mol/L;
the La (NO)3)3The pH of the solution was adjusted to 10.
6. The method of claim 1, wherein in step S3, the attapulgite heat activated materials PAL-H and La (OH)3The mass ratio of (1): 1-1: 1.6.
7. the preparation method according to claim 4, wherein in step S3, the reaction time under the action of ultrasound is 10-30 min, and the reaction time under the water bath condition is 5-10 h;
the temperature of the water bath is 60-70 ℃.
8. The method according to claim 4, wherein in step S3, the precipitate is dried at 60-80 ℃ for 12-48 h;
grinding the precipitate, and sieving with 200 mesh sieve to obtain the lanthanum-loaded attapulgite composite PAL-La.
9. The application of the lanthanum-loaded attapulgite composite PAL-La prepared by the preparation method of any one of claims 1 to 8, which is characterized in that the lanthanum-loaded attapulgite composite PAL-La is used for adsorbing phosphate;
the adsorption rate of the lanthanum attapulgite composite PAL-La on a solution with the phosphate concentration below 50mg/L and the pH range of 3-11 is more than or equal to 99%.
10. The use according to claim 9, wherein the lanthanum attapulgite composite PAL-La is used to adsorb phosphate in a competitive anion environment;
the competing anion comprises SO4 2-、NO3 -、HCO3 -And Cl-。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110252297.0A CN113041991A (en) | 2021-03-08 | 2021-03-08 | Preparation method and application of lanthanum-loaded attapulgite phosphorus removal adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110252297.0A CN113041991A (en) | 2021-03-08 | 2021-03-08 | Preparation method and application of lanthanum-loaded attapulgite phosphorus removal adsorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113041991A true CN113041991A (en) | 2021-06-29 |
Family
ID=76510483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110252297.0A Pending CN113041991A (en) | 2021-03-08 | 2021-03-08 | Preparation method and application of lanthanum-loaded attapulgite phosphorus removal adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113041991A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907058A (en) * | 2022-04-15 | 2022-08-16 | 浙江碧水量子科技有限公司 | Water purification component for reducing total phosphorus and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817439A (en) * | 2006-01-17 | 2006-08-16 | 昆明理工大学 | Rare earth adsorbent and production thereof |
| CN103723785A (en) * | 2013-12-13 | 2014-04-16 | 陕西科技大学 | Method adopting lanthanum modified attapulgite to remove fluorinion in water |
| CN105903431A (en) * | 2016-05-10 | 2016-08-31 | 西安建筑科技大学 | Lanthanum-loaded modified bentonite fluorine removal material as well as preparation method and application method thereof |
| CN110038511A (en) * | 2018-01-17 | 2019-07-23 | 华中科技大学 | A kind of preparation method and applications carrying lanthanum modified alta-mud dephosphorization material |
| CN110193342A (en) * | 2019-06-12 | 2019-09-03 | 明光市飞洲新材料有限公司 | A kind of modified attapulgite earth adsorbing and preparation method thereof |
| CN110548490A (en) * | 2018-05-31 | 2019-12-10 | 华中科技大学 | Preparation method and application of recyclable lanthanum modified bentonite phosphorus removal material |
-
2021
- 2021-03-08 CN CN202110252297.0A patent/CN113041991A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817439A (en) * | 2006-01-17 | 2006-08-16 | 昆明理工大学 | Rare earth adsorbent and production thereof |
| CN103723785A (en) * | 2013-12-13 | 2014-04-16 | 陕西科技大学 | Method adopting lanthanum modified attapulgite to remove fluorinion in water |
| CN105903431A (en) * | 2016-05-10 | 2016-08-31 | 西安建筑科技大学 | Lanthanum-loaded modified bentonite fluorine removal material as well as preparation method and application method thereof |
| CN110038511A (en) * | 2018-01-17 | 2019-07-23 | 华中科技大学 | A kind of preparation method and applications carrying lanthanum modified alta-mud dephosphorization material |
| CN110548490A (en) * | 2018-05-31 | 2019-12-10 | 华中科技大学 | Preparation method and application of recyclable lanthanum modified bentonite phosphorus removal material |
| CN110193342A (en) * | 2019-06-12 | 2019-09-03 | 明光市飞洲新材料有限公司 | A kind of modified attapulgite earth adsorbing and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LINGCHAO KONG ET AL.: "Highly-effective phosphate removal from aqueous solutions by calcined nano-porous palygorskite matrix with embedded lanthanum hydroxide", 《APPLIED CLAY SCIENCE》 * |
| 苗琛琛等: "镧改性凹凸棒土的制备及其对水中磷酸盐的吸附", 《环境工程学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907058A (en) * | 2022-04-15 | 2022-08-16 | 浙江碧水量子科技有限公司 | Water purification component for reducing total phosphorus and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109513424B (en) | Carbon/hydrotalcite composite adsorbent, preparation thereof, application of carbon/hydrotalcite composite adsorbent in heavy metal adsorption and regeneration method | |
| US20220219142A1 (en) | Polymeric lanthanum nanocomposite, and preparation method and application thereof | |
| CN104888748A (en) | Modified meerschaum, preparation method and application thereof | |
| CN111420630A (en) | Preparation and regeneration method of magnesium hydroxide modified diatomite dephosphorizing agent | |
| CN110975821A (en) | Silicon dioxide and calcium alginate composite metal ion adsorbent, preparation method and application | |
| CN111905690A (en) | Method for preparing water body nitrogen and phosphorus removal oxygenation composite material by utilizing coal ash | |
| CN113426402B (en) | Preparation method and application of lanthanum-aluminum multi-element composite mineral phosphorus removal material | |
| CN110394154B (en) | Preparation method and application of moso bamboo charcoal/FeMn-LDH composite material | |
| Ji et al. | A review of metallurgical slag for efficient wastewater treatment: pretreatment, performance and mechanism | |
| CN113041991A (en) | Preparation method and application of lanthanum-loaded attapulgite phosphorus removal adsorbent | |
| CN113387394A (en) | Preparation method of layered double-metal hydroxide material based on biobased calcium carbonate | |
| CN113134339A (en) | Preparation of zirconium-doped hydrotalcite-like adsorbent and application of zirconium-doped hydrotalcite-like adsorbent in treatment of phosphorus-containing wastewater | |
| CN110681344B (en) | Zirconium series nano hybrid material and application method thereof | |
| CN100537442C (en) | Method for preparing sewage water additive by intermediate product of diatomite purification | |
| CN113000015A (en) | Preparation method and dephosphorization application of attapulgite-periclase-based hydrotalcite | |
| CN105036216A (en) | Sodium-manganese water purifying material as well as preparation method and application thereof | |
| CN112934170A (en) | Magnetic nano-ore composite material for efficiently removing thallium, and preparation method and application thereof | |
| CN107540081B (en) | Preparation method of composite biological filler for biochemical treatment of sewage | |
| Wu et al. | Adsorption removal of Mn 2+ and NH 4+–N from electrolytic manganese metal wastewater by modified phosphate ore flotation tailings | |
| Li et al. | Removal of NH+ 4-N from aqueous solution by ceramsite coated with Mg (OH) 2 combined with air stripping. | |
| CN101015788A (en) | Ferrum-silicon modified alta-mud for water treatment and its preparation method | |
| CN112619598B (en) | Water phosphorus adsorbent and preparation method and application thereof | |
| CN113694965B (en) | Flower-shaped composite photocatalytic material with stem and preparation method and application thereof | |
| Wang et al. | Assessment of the induced effect of selected iron hydroxysulfates biosynthesized using Acidithiobacillus ferrooxidans for biomineralization of acid mine drainage | |
| CN108101144B (en) | Method for activating colloidal particles extracted from sediments and application of method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210629 |