CN104667874A - Preparation method of hydroxyapatite modified compound heavy metal adsorbent with eucalyptus structure - Google Patents
Preparation method of hydroxyapatite modified compound heavy metal adsorbent with eucalyptus structure Download PDFInfo
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- CN104667874A CN104667874A CN201510086083.5A CN201510086083A CN104667874A CN 104667874 A CN104667874 A CN 104667874A CN 201510086083 A CN201510086083 A CN 201510086083A CN 104667874 A CN104667874 A CN 104667874A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 39
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 26
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 244000166124 Eucalyptus globulus Species 0.000 title claims abstract 9
- 239000003463 adsorbent Substances 0.000 title abstract description 11
- 150000001875 compounds Chemical class 0.000 title abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000002250 absorbent Substances 0.000 claims description 21
- 230000002745 absorbent Effects 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 19
- 230000029087 digestion Effects 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000004567 concrete Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000002023 wood Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000003607 modifier Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 241000196324 Embryophyta Species 0.000 abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 abstract 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 abstract 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 abstract 1
- 235000019838 diammonium phosphate Nutrition 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 241000219927 Eucalyptus Species 0.000 description 28
- 239000000243 solution Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000003484 anatomy Anatomy 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003462 bioceramic Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a hydroxyapatite modified compound heavy metal adsorbent with a eucalyptus structure. By fully utilizing the advantage of a multistage porous structure of eucalyptus, the compound heavy metal adsorbent is obtained by fully changing the structural components of hydroxyapatite by an in-situ synthesis method and is applied to highly efficient adsorption purification treatment of cadmium and lead in a water environment. The method can be used for controlling micropollution caused by heavy metals in the water environment and reducing heavy metals in smelting wastewater. The method is characterized by mainly utilizing low-concentration (NH4)2HPO4 and a saturated Ca(OH)2 solution as basic liquids and adopting the in-situ synthesis technology to generate a modifier to prepare the compound heavy metal adsorbent with the eucalyptus structure. The hydroxyapatite modified compound heavy metal adsorbent with the eucalyptus structure and natural plant structure morphology is synthesized by manually controlling the preparation process. The preparation method has the beneficial effects that a cheap and environment-friendly material is provided for heavy metal pollution control; a new method and approach is provided for utilization of eucalyptus wood; and the compound heavy metal adsorbent has the advantages of good adsorption effects, wide range of application, simplicity and stability in material preparation, easier process, and the like.
Description
Technical field
The invention belongs to changing waste into resources to utilize and water-treatment technology field, particularly a kind of preparation method of hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent.The method utilizes hydroxyapatite for modifier, through the technology controlling and process of situ synthesis techniques, and the heavy metal composite adsorbent that to prepare with hydroxyapatite and carbon be main component.
Background technology
The toxic element that a class can be accumulated in vivo with the heavy metal that plumbous, cadmium are representative, meeting Cumulate Sum enrichment in biological chain after its entered environment, and can not be biodegradable, can hide in the environment for a long time, and enter human body serious harm life and health with food chain.Along with socioeconomic development, heavy metal pollution is in widespread attention, in current water, the minimizing technology of heavy metal mainly contains chemical precipitation method, electroflotation, ion-exchange, membrane separation process and absorption method, and wherein absorption method has the advantages such as instant effect, renewable recovery, secondary pollution probability be low and attention due to it.
The intrinsic structure of multi-level, multidimensional, many structures of wood structure to be nature through 1 years develop self-assembling formation, its structural constituent is changed by in-situ synthetic method, can prepare and both keep nature biotechnology fine structure, pass through selectively environment functional material again.
At present, the most frequently used adsorbent has activated carbon and modified cellulose etc., but mostly adsorbent is because cost is high, complex manufacturing or heavy metal are adsorbed length consuming time and limited its application.Researchers both domestic and external possess different tendency function sorbing material with different fibrous materials (as cotton, rice husk, jute, paper products etc.) for Template preparation obtains in trial.Scholar is had to utilize aminobenzenesulfonic acid, citric acid and molysite etc. to be modifier; modification is carried out to before and after wood materials charing; prepare the Carbon Materials with loose structure; material can have very strong adsorption activity through special surface process; can be applicable to water body purification; improve living environment, the fields such as environmental protection such as electromagnetic wave shielding.
Hydroxyapatite hydroxyapatite metal surface active material, it has similar chemical composition and structure to organism sclerous tissues, there is good biocompatibility and biologically active, it is good bioceramic material, but its mechanical property still has some deficits, for the manufacture of the sorbing material of the special gap structure of tool, be difficult to meet the destruction tolerances of liquid by washing away.
Eucalyptus is one of large quick growing species of trees in the world three.The cultivated area of China eucalyptus in 2010 has reached 2,670,000 hectares, and growing stock amount surpasses 6,000 ten thousand square metres, occupies third place in the world.At present paper pulp processed mainly concentrated on to the utilization of eucalyptus, make on fiber and glued board; and mainly utilize eucalyptus bodywood; eucalyptus root and branch to be abandoned or as firewood usually using upper part; these parts are as recyclability waste material; if dealt with improperly, not only can cause the wasting of resources, more can form pollution; bring pressure to environmental protection, be unfavorable for the sustainable development of ecological environment.In addition, Eucalyptus Wood has the ordered porous special anatomical structure of different scale scope, the existence of pit membrane and torus, pit is made not to be a kind of natural perforate, easily the Jin Tian soma of guide hole in timber can be removed by the pretreatment of suitable digestion agent, increase considerably the three-dimensional network waiting to try Eucalyptus Wood internal structure connective, improve later stage saturating machine, improve the network connectivty of product simultaneously, be beneficial to preparation plant templated porous sorbing material.
Summary of the invention
The object of this invention is to provide a kind of preparation method of hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent.To obtained adsorbent carry out thing phase with structure, become to be grouped into and shape characteristic Experimental Characterization, and be applied to the adsorption treatment of water environment common heavy metal element, for Heavy Metal Pollution Control provides a kind of cheapness and eco-friendly material, provide a kind of new method, new way for Eucalyptus Wood utilizes.
The thinking of the inventive method: with low concentration (NH
4)
2hP0
4with saturated Ca (OH)
2liquid based on solution, situ synthesis techniques is adopted to generate modifier, preparation obtains Eucalyptus structure composite heavy metal absorbent, and by Artificial Control preparation technology, synthesis has the hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent of natural plants structural form.
Concrete steps are:
(1) by eucalyptus root or the peeling of limb timber, dry.
(2) dose volume concentration is that the weak aqua ammonia of 5 ~ 8% is as digestion agent.
(3) (the NH of 0.02 ~ 0.05mo1/L is prepared respectively
4)
2hP0
4solution and saturated Ca (OH)
2solution is as fabricated in situ basal liquid.
(4) product that step (1) obtains is placed in the digestion agent that step (2) obtains, under 100 ~ 110 DEG C of conditions, digestion 6 ~ 8 hours, completes extracting pretreatment.
(5) product ultra-pure water step (4) obtained is cleaned, and is roasting 3 ~ 4 hours in the Muffle furnace of 400 ~ 500 DEG C in temperature, and stove is chilled to room temperature.
(6) product that step (5) obtains is immersed in the saturated Ca (OH) that step (3) obtains
2in solution, and 25 ~ 35 DEG C of water-bath inside holding 24 ~ 48 hours.
(7) by (NH that the product that step (6) obtains obtains in step (3)
4)
2hP0
4soak 2 hours in solution, then taking-up product is immersed in the saturated Ca (OH) that step (3) obtains
2solution 2 hours, sample all uses ultrapure water 19 ~ 21 seconds after each immersion, and is placed in 50 DEG C of drying in oven 2 hours.
(8) step (7) four times are repeated.
(9) product that step (8) obtains is ground, cross 100 ~ 150 mesh sieves, be i.e. obtained hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent.
The inventive method is simple for process, preparation process low cost, and owing to utilizing Eucalyptus Wood, lime stone etc. to be main raw material(s), material is easy to get, and through technology controlling and process, substantially increases the absorption property of material heavy metal; The product of gained can be widely used in heavy metal pollution water treatment.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram (FI-IR) of the hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent that the embodiment of the present invention obtains.
Fig. 2 is the X-ray diffractogram (XRD) of the hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent that the embodiment of the present invention obtains.
Fig. 3 is the SEM microscopy figure (SEM, × 100 times) of the hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent that the embodiment of the present invention obtains.
Fig. 4 is the SEM microscopy figure (SEM, × 1000 times) of the hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent that the embodiment of the present invention obtains.
Fig. 5 is that the obtained hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent of the embodiment of the present invention is to the Adsorption Effect variation diagram of three kinds of variable concentrations cadmiums (II) in different initial pH value Water Under solution.
Fig. 6 is that the obtained hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent of the embodiment of the present invention is to the Adsorption Effect variation diagram of different dosage to three kinds of lead at different concentrations (II) in the aqueous solution.
Detailed description of the invention
embodiment:
One, the preparation of hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent
(1) removed the peel by eucalyptus root timber 1kg, after dry, cut lengths are about: the blocks of length × wide × height=30mm × 10mm × 3mm.
(2) dose volume concentration is that the weak aqua ammonia of 5% is as digestion agent.
(3) (the NH of 0.02mo1/L is prepared respectively
4)
2hP0
4solution and saturated Ca (OH)
2solution is as fabricated in situ basal liquid.
(4) product that step (1) obtains is placed in the digestion agent that step (2) obtains, under 105 DEG C of conditions, digestion 7 hours, completes extracting pretreatment.
(5) the product ultra-pure water that step (4) obtains is cleaned, and be roasting 3 hours in the Muffle furnace of 500 DEG C in temperature, and stove is chilled to room temperature.
(6) product that step (5) obtains is immersed in the saturated Ca (OH) that step (3) obtains
2in solution, and 25 DEG C of water-bath inside holding 48 hours.
(7) by (NH that the product that step (6) obtains obtains in step (3)
4)
2hP0
4soak 2 hours in solution, then taking-up product is immersed in the saturated Ca (OH) that step (3) obtains
2solution 2 hours, sample all uses ultrapure water 20 seconds after each immersion, and is placed in 50 DEG C of drying in oven 2 hours.
(8) step (7) four times are repeated.
(9) product that step (8) obtains is ground, cross 100 ~ 150 mesh sieves, be i.e. obtained hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent.
The thing phase of the hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent that the present embodiment is obtained and structure, become to be grouped into and shape characteristic adopts X-ray diffractometer (XRD, X'Pert PRO), ftir Analysis is used in conjunction system (STA-449C; 470 FT-IR) energy disperse spectroscopy and SEM (SEM, JSM-6380LV) carry out observation test, specifically sees Figure of description 1,2,3 and 4.
Two, heavy metal absorbent is to the adsorption effect of cadmium (II)
(1) CdNO is used
3(analyzing pure) compound concentration is each 8 bottles of cadmium (II) the pending liquid of 5mg/L, 10mg/L and 50mg/L, uses HNO
3respectively the pH value of pending liquid is adjusted to 1.0,2.0,3.0,4.0,5.0,6.0,7.0 and 8.0 with NaOH.
(2) the pending liquid numbering pipetting 50ml step (1) respectively obtained is bottled for subsequent use in 100ml centrifuge tube.
(3) the hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent that 0.1g the present embodiment is obtained is added in the pending liquid of step (2) centrifuge tube for subsequent use respectively, seal 25 DEG C of constant temperature oscillations that laggard line of hitch oscillator frequency is 150r/min, duration of oscillation is 6 hours.
(4) product getting step (3) crosses 0.22 μm of miillpore filter, use cadmium (II) concentration of Flame Atomic Absorption Spectrometry Determination remnants, obtaining product under pH value is 1.0,2.0,3.0,4.0,5.0,6.0,7.0 and 8.0 conditions is the pending liquid adsorption effect of cadmium (II) of 5mg/L, 10mg/L and 50mg/L to concentration, as shown in Figure 4.
Three, heavy metal absorbent is to the adsorption effect of plumbous (II)
(1) Pb (NO is used
3)
2(top grade is pure) compound concentration is each 10 bottles of lead (II) the pending liquid of 5mg/L, 10mg/L and 50mg/L, uses HNO
3with NaOH, the pH value of pending liquid is adjusted to 5.0.
(2) the pending liquid numbering pipetting 50ml step (1) respectively obtained is bottled for subsequent use in 100ml centrifuge tube.
(3) 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 and the obtained hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent of 1.0g the present embodiment is added in the pending liquid of step (2) centrifuge tube for subsequent use respectively, seal 25 DEG C of constant temperature oscillations that laggard line of hitch oscillator frequency is 150r/min, duration of oscillation is 6 hours.
(4) product getting step (3) crosses 0.22 μm of miillpore filter, use lead (II) concentration of Flame Atomic Absorption Spectrometry Determination remnants, obtain adsorbent dosage be 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 and 1.0g condition under product be the pending liquid adsorption effect of lead (II) of 5mg/L, 10mg/L and 50mg/L to concentration, as shown in Figure 5.
Claims (1)
1. a preparation method for hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent, is characterized in that concrete steps are:
(1) by eucalyptus root or the peeling of limb timber, dry;
(2) dose volume concentration is that the weak aqua ammonia of 5 ~ 8% is as digestion agent;
(3) (the NH of 0.02 ~ 0.05mo1/L is prepared respectively
4)
2hP0
4solution and saturated Ca (OH)
2solution is as fabricated in situ basal liquid;
(4) product that step (1) obtains is placed in the digestion agent that step (2) obtains, under 100 ~ 110 DEG C of conditions, digestion 6 ~ 8 hours, completes extracting pretreatment;
(5) product ultra-pure water step (4) obtained is cleaned, and is roasting 3 ~ 4 hours in the Muffle furnace of 400 ~ 500 DEG C in temperature, and stove is chilled to room temperature;
(6) product that step (5) obtains is immersed in the saturated Ca (OH) that step (3) obtains
2in solution, and 25 ~ 35 DEG C of water-bath inside holding 24 ~ 48 hours;
(7) by (NH that the product that step (6) obtains obtains in step (3)
4)
2hP0
4soak 2 hours in solution, then taking-up product is immersed in the saturated Ca (OH) that step (3) obtains
2solution 2 hours, sample all uses ultrapure water 19 ~ 21 seconds after each immersion, and is placed in 50 DEG C of drying in oven 2 hours;
(8) step (7) four times are repeated;
(9) product that step (8) obtains is ground, cross 100 ~ 150 mesh sieves, be i.e. obtained hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106111067A (en) * | 2016-07-27 | 2016-11-16 | 中国科学院新疆理化技术研究所 | A kind of preparation method and application of silane coupler modified magnetic halloysite material |
| CN106268634A (en) * | 2016-08-09 | 2017-01-04 | 江苏陆博环保科技有限公司 | Preparation method for the inorganic compound particles of effluent containing heavy metal ions advanced treating |
| CN108636339A (en) * | 2018-04-26 | 2018-10-12 | 桂林理工大学 | The preparation method of hydroxyapatite modified moso bamboo structure composite heavy metal absorbent |
| CN111229156A (en) * | 2020-01-20 | 2020-06-05 | 齐鲁工业大学 | Preparation and application of hydroxyapatite modified mesoporous silica adsorption material |
| CN111495315A (en) * | 2020-04-23 | 2020-08-07 | 齐鲁工业大学 | Pb in water body2+Application and preparation method of adsorbing material |
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| CN102895957A (en) * | 2012-11-11 | 2013-01-30 | 桂林理工大学 | Preparation method of moso bamboo biomorphic Fe2O3/Fe3O4 compound heavy metal absorbent |
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| CN106111067A (en) * | 2016-07-27 | 2016-11-16 | 中国科学院新疆理化技术研究所 | A kind of preparation method and application of silane coupler modified magnetic halloysite material |
| CN106111067B (en) * | 2016-07-27 | 2018-10-26 | 中国科学院新疆理化技术研究所 | A kind of preparation method and application of silane coupler modified magnetic halloysite material |
| CN106268634A (en) * | 2016-08-09 | 2017-01-04 | 江苏陆博环保科技有限公司 | Preparation method for the inorganic compound particles of effluent containing heavy metal ions advanced treating |
| CN108636339A (en) * | 2018-04-26 | 2018-10-12 | 桂林理工大学 | The preparation method of hydroxyapatite modified moso bamboo structure composite heavy metal absorbent |
| CN108636339B (en) * | 2018-04-26 | 2021-05-25 | 桂林理工大学 | Preparation method of hydroxyapatite modified moso bamboo structure composite heavy metal adsorbent |
| WO2021007986A1 (en) * | 2019-07-12 | 2021-01-21 | 华南理工大学 | Carboxylated banyan aerial root fiber adsorbent and preparation method therefor and application thereof |
| CN111229156A (en) * | 2020-01-20 | 2020-06-05 | 齐鲁工业大学 | Preparation and application of hydroxyapatite modified mesoporous silica adsorption material |
| CN111229156B (en) * | 2020-01-20 | 2021-07-13 | 齐鲁工业大学 | Preparation and application of hydroxyapatite modified mesoporous silica adsorption material |
| CN111495315A (en) * | 2020-04-23 | 2020-08-07 | 齐鲁工业大学 | Pb in water body2+Application and preparation method of adsorbing material |
| CN111495315B (en) * | 2020-04-23 | 2021-05-25 | 齐鲁工业大学 | Pb in water body2+Application and preparation method of adsorbing material |
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