CN104667873A - Preparation method of hydroxyapatite modified towel gourd vegetable sponge biomorphic heavy metal adsorbent - Google Patents
Preparation method of hydroxyapatite modified towel gourd vegetable sponge biomorphic heavy metal adsorbent Download PDFInfo
- Publication number
- CN104667873A CN104667873A CN201510086076.5A CN201510086076A CN104667873A CN 104667873 A CN104667873 A CN 104667873A CN 201510086076 A CN201510086076 A CN 201510086076A CN 104667873 A CN104667873 A CN 104667873A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- obtains
- hours
- preparation
- solution
- 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.)
- Granted
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a hydroxyapatite modified towel gourd vegetable sponge biomorphic heavy metal adsorbent. By utilizing the advantage of a multistage porous structure of towel gourd vegetable sponge, 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 heavy metals in a water environment, such as cadmium. 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 prepare the compound heavy metal adsorbent with a eucalyptus structure. The hydroxyapatite modified towel gourd vegetable sponge biomorphic compound heavy metal adsorbent with 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 the agricultural waste, namely towel gourd vegetable sponge; and the 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 the preparation method of state structure heavy metal absorbent lost by a kind of hydroxyapatite modified luffa.The method utilizes luffa for plant template, through technology controlling and process, and the heavy metal composite adsorbent that to prepare with hydroxyapatite and activated carbon be main material.
Background technology
Heavy metal is a kind of toxic element that can accumulate in vivo, along with industrial expansion, heavy metal pollution is in widespread attention, meeting Cumulate Sum enrichment in biological chain after heavy metal 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.In current water, the place to go method of heavy metal mainly contains chemical precipitation method, electroflotation, ion-exchange, membrane separation process and absorption method, the advantages such as wherein absorption method does not produce secondary pollution because it has, renewable recovery and attention.At present, the most frequently used adsorbent has activated carbon and modified cellulose etc., but mostly adsorbent is because cost is high or complex manufacturing and limit its application.
Morph-genetic materials uses that nature is multi-level through the biology self of 1 years, the intrinsic structure of multidimensional, many structures, by manual method, change its structural constituent, prepare and both keep nature biotechnology fine structure, pass through selectively compound again, the artificial material giving characteristic and function.The mechanism of plant template is mainly introduced the synthesis of inorganic material and the preparation of composite by it, with natural plants structure for template, prepare and various there is distinct plant structure feature, unique microstructure institutional framework is controlled, physical and mechanical properties is controlled ordered porous inorganic fibers, thus prepare the morph-genetic materials with the high comprehensive performance that string ecological ceramic and metal material have.
At present, researchers both domestic and external are attempting with different fibrous materials (as eucalyptus, mao bamboon, cotton, rice husk, jute, paper products etc.) as Template preparation obtains the something lost state porous oxide possessing different tendency function.Control to be the Carbon Materials with loose structure by plant structure material converting by charring process; this 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 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.
Luffa (
vegetable Sponge of Luffa) another name vegetable sponge, sponge gourd cloth, being plant sponge abroad, is the sponge gourd fruit vascular bundle of the aging rear peeling of cucurbitaceous plant sponge gourd and seed, apparent many in long prismatic or oval tubular, slightly bending, length 30 ~ 70cm, diameter 7 ~ 10cm.Surface yellowish white.Body is light, and matter is tough, flexible, can not fracture.Visible ovary 3 Room, cross section, in empty shape, the inside has reticular fibre to enrich, and single reticular fibre has the ordered porous special anatomical structure of different scale scope, can the Jin Tian soma of guide hole in single reticular fibre be removed easily by the pretreatment of suitable digestion agent, the three-dimensional network increasing considerably luffa reticular fibre internal structure is connective, improves later stage saturating machine, improve the network connectivty of product simultaneously, be beneficial to and prepare porous adsorbing material.
Summary of the invention
The object of this invention is to provide the preparation method that state structure heavy metal absorbent lost by a kind of hydroxyapatite modified luffa.To obtained heavy metal absorbent 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, the utilization for agricultural wastes luffa provides a kind of new method, new way.
The thinking of the inventive method: with low concentration (NH
4)
2hP0
4with saturated Ca (OH)
2liquid based on solution, adopt situ synthesis techniques preparation to obtain luffa and lose state structure composite heavy metal absorbent, by Artificial Control preparation technology, make the hydroxyapatite modified luffa with natural plants structural form and lose state structure composite heavy metal absorbent.
Concrete steps are:
(1) naturally dried by luffa, peeling, remove seed, fragmentation is 15 × 15 × 15mm
3the block of size.
(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) block that step (1) obtains is placed in the digestion agent that step (2) obtains, at 100 ~ 110 DEG C, digestion 6 ~ 8 hours, completes extracting pretreatment.
(5) product ultra-pure water step (4) obtained is cleaned and to be placed under 80 DEG C of environment dry 24 hours, and is roasting 2 ~ 3 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 at the water-bath inside holding 24 ~ 48 hours of 25 ~ 35 DEG C.
(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) five times are repeated.
(9) ground by the product that step (8) obtains, cross 100 ~ 150 mesh sieves, namely state structure heavy metal absorbent lost by obtained hydroxyapatite modified luffa.
The inventive method is simple for process, preparation process low cost, and owing to utilizing luffa, 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 luffa something lost state structure heavy metal absorbent that the embodiment of the present invention obtains.
Fig. 2 is the X-ray diffractogram (XRD) of the hydroxyapatite modified luffa something lost state structure heavy metal absorbent that the embodiment of the present invention obtains.
Fig. 3 is the SEM microscopy figure (SEM, × 30 times) of the hydroxyapatite modified luffa something lost state structure heavy metal absorbent that the embodiment of the present invention obtains.
Fig. 4 is the SEM microscopy figure (SEM, × 500 times) of the hydroxyapatite modified luffa something lost state structure heavy metal absorbent that the embodiment of the present invention obtains.
Fig. 5 is that the hydroxyapatite modified luffa that the embodiment of the present invention obtains loses state structure heavy metal absorbent to the Adsorption Effect variation diagram of three kinds of variable concentrations cadmiums (II) in different initial pH value Water Under solution.
Detailed description of the invention
embodiment:
One, the preparation of state structure heavy metal absorbent lost by hydroxyapatite modified luffa
(1) naturally dried by luffa one, peeling, remove seed, fragmentation is 15 × 15 × 15mm
3the block of size.
(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) block that step (1) obtains is placed in the digestion agent that step (2) obtains, at 105 DEG C, digestion 7 hours, completes extracting pretreatment.
(5) product ultra-pure water step (4) obtained is cleaned and to be placed under 80 DEG C of environment dry 24 hours, and is roasting 2 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 at the water-bath inside holding 48 hours of 25 DEG C.
(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) five times are repeated.
(9) ground by the product that step (8) obtains, cross 100 ~ 150 mesh sieves, namely state structure heavy metal absorbent lost by obtained hydroxyapatite modified luffa.
Hydroxyapatite modified luffa that the present embodiment the is obtained thing phase of losing state structure composite heavy metal absorbent 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 1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0 and 9.0 with NaOH.
(2) the pending liquid numbering pipetting 50ml step (1) respectively obtained is bottled for subsequent use in 100ml centrifuge tube.
(3) add the obtained hydroxyapatite modified luffa of 0.1g the present embodiment in the pending liquid of step (2) centrifuge tube for subsequent use respectively and lose state structure heavy metal absorbent, 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 1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0 and 9.0 conditions is the pending liquid adsorption effect of cadmium (II) of 5mg/L, 10mg/L and 50mg/L to concentration, specifically sees Figure of description 5.
Claims (1)
1. a preparation method for state structure heavy metal absorbent lost by hydroxyapatite modified luffa, it is characterized in that concrete steps are:
(1) naturally dried by luffa, peeling, remove seed, fragmentation is 15 × 15 × 15mm
3the block of size;
(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) block that step (1) obtains is placed in the digestion agent that step (2) obtains, at 100 ~ 110 DEG C, digestion 6 ~ 8 hours, completes extracting pretreatment;
(5) product ultra-pure water step (4) obtained is cleaned and to be placed under 80 DEG C of environment dry 24 hours, and is roasting 2 ~ 3 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 at the water-bath inside holding 24 ~ 48 hours of 25 ~ 35 DEG C;
(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) five times are repeated;
(9) ground by the product that step (8) obtains, cross 100 ~ 150 mesh sieves, namely state structure heavy metal absorbent lost by obtained hydroxyapatite modified luffa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510086076.5A CN104667873B (en) | 2015-02-21 | 2015-02-21 | Preparation method of hydroxyapatite modified towel gourd vegetable sponge biomorphic heavy metal adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510086076.5A CN104667873B (en) | 2015-02-21 | 2015-02-21 | Preparation method of hydroxyapatite modified towel gourd vegetable sponge biomorphic heavy metal adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104667873A true CN104667873A (en) | 2015-06-03 |
| CN104667873B CN104667873B (en) | 2017-04-12 |
Family
ID=53303773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510086076.5A Active CN104667873B (en) | 2015-02-21 | 2015-02-21 | Preparation method of hydroxyapatite modified towel gourd vegetable sponge biomorphic heavy metal adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104667873B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569878A (en) * | 2020-05-25 | 2020-08-25 | 哈尔滨工业大学 | Preparation method and application of loofah sponge genetic porous carbon supported Fenton-like catalyst |
| CN112871134A (en) * | 2021-01-18 | 2021-06-01 | 重庆大学 | Cu-HAP-biochar composite material for adsorbing hydrogen sulfide and preparation method thereof |
| CN113213632A (en) * | 2021-06-15 | 2021-08-06 | 萍乡学院 | Nano-hydroxyapatite loofah sponge composite filler and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6270212A (en) * | 1985-09-23 | 1987-03-31 | Toa Nenryo Kogyo Kk | Calcium phosphate based hydroxyapatite and production thereof |
| KR100334934B1 (en) * | 1999-05-19 | 2002-05-04 | 이한종 | Method of producing an aggregating agent for better environment |
| CN101239306A (en) * | 2008-03-18 | 2008-08-13 | 上海大学 | Method for preparing etherification luffa and application of it in metallic ion adsorption |
| CN101773817A (en) * | 2009-01-13 | 2010-07-14 | 厦门绿邦膜技术有限公司 | Composite absorption material for wastewater treatment and preparation method thereof |
| CN102258976A (en) * | 2011-05-20 | 2011-11-30 | 桂林理工大学 | Preparation method of eucalyptus biomorphic Fe2O3/Fe3O4 composite heavy metal adsorbent |
| CN102381691A (en) * | 2011-07-29 | 2012-03-21 | 沈阳大学 | Preparation method of nano hydroxylapatite adsorbent for absorbing heavy metal ions in waste water |
| CN102380350A (en) * | 2011-10-24 | 2012-03-21 | 上海海洋大学 | Method for removing hydroxyapatite modified eggshell adsorbent material and recycling phosphate from wastewater |
| CN103861567A (en) * | 2014-03-21 | 2014-06-18 | 桂林理工大学 | Preparation method of hydroxyapatite/bagasse active carbon |
-
2015
- 2015-02-21 CN CN201510086076.5A patent/CN104667873B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6270212A (en) * | 1985-09-23 | 1987-03-31 | Toa Nenryo Kogyo Kk | Calcium phosphate based hydroxyapatite and production thereof |
| KR100334934B1 (en) * | 1999-05-19 | 2002-05-04 | 이한종 | Method of producing an aggregating agent for better environment |
| CN101239306A (en) * | 2008-03-18 | 2008-08-13 | 上海大学 | Method for preparing etherification luffa and application of it in metallic ion adsorption |
| CN101773817A (en) * | 2009-01-13 | 2010-07-14 | 厦门绿邦膜技术有限公司 | Composite absorption material for wastewater treatment and preparation method thereof |
| CN102258976A (en) * | 2011-05-20 | 2011-11-30 | 桂林理工大学 | Preparation method of eucalyptus biomorphic Fe2O3/Fe3O4 composite heavy metal adsorbent |
| CN102381691A (en) * | 2011-07-29 | 2012-03-21 | 沈阳大学 | Preparation method of nano hydroxylapatite adsorbent for absorbing heavy metal ions in waste water |
| CN102380350A (en) * | 2011-10-24 | 2012-03-21 | 上海海洋大学 | Method for removing hydroxyapatite modified eggshell adsorbent material and recycling phosphate from wastewater |
| CN103861567A (en) * | 2014-03-21 | 2014-06-18 | 桂林理工大学 | Preparation method of hydroxyapatite/bagasse active carbon |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569878A (en) * | 2020-05-25 | 2020-08-25 | 哈尔滨工业大学 | Preparation method and application of loofah sponge genetic porous carbon supported Fenton-like catalyst |
| CN111569878B (en) * | 2020-05-25 | 2022-04-29 | 哈尔滨工业大学 | Preparation method and application of loofah sponge genetic porous carbon supported Fenton-like catalyst |
| CN112871134A (en) * | 2021-01-18 | 2021-06-01 | 重庆大学 | Cu-HAP-biochar composite material for adsorbing hydrogen sulfide and preparation method thereof |
| CN112871134B (en) * | 2021-01-18 | 2022-04-15 | 重庆大学 | Cu-HAP-biochar composite material for adsorbing hydrogen sulfide and preparation method thereof |
| CN113213632A (en) * | 2021-06-15 | 2021-08-06 | 萍乡学院 | Nano-hydroxyapatite loofah sponge composite filler and preparation method and application thereof |
| CN113213632B (en) * | 2021-06-15 | 2022-11-25 | 萍乡学院 | Nano-hydroxyapatite loofah sponge composite filler and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104667873B (en) | 2017-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102258976B (en) | Preparation method of eucalyptus biomorphic Fe2O3/Fe3O4 composite heavy metal adsorbent | |
| CN104667874B (en) | The preparation method of hydroxyapatite modified Eucalyptus structure composite heavy metal absorbent | |
| CN102895957B (en) | Preparation method of moso bamboo biomorphic Fe2O3/Fe3O4 compound heavy metal absorbent | |
| CN105236507B (en) | The method that the adsorbent being combined using beta cyclodextrin chitosan and walnut shell charcoal removes the Cr VI in waste water | |
| CN105170091A (en) | Preparation method of iron-modified reed biological carbon, and application of iron-modified reed biological carbon in treatment of phosphorus wastewater | |
| CN103212378B (en) | Preparation method and application of citric acid modified palm tree bark adsorbing agent | |
| CN103736442B (en) | A kind of biological template legal system is for the method for porous oxidation aluminium composite material | |
| CN110041016A (en) | A kind of geo-polymer adsorbent material and preparation method thereof | |
| CN104667873B (en) | Preparation method of hydroxyapatite modified towel gourd vegetable sponge biomorphic heavy metal adsorbent | |
| CN100453167C (en) | Method for preparing mesoporous titanium dioxide optical catalyst using plant peels and films | |
| CN103100369A (en) | Method for preparing matrix for household sewage biological treatment technology by using rice husk activated carbon | |
| CN110433772A (en) | A kind of preparation method and application of mulberry tree bar charcoal/Fe-Mn compound adsorbent | |
| Jin et al. | Duck feather/nonwoven composite fabrics for removing metals present in textile dyeing effluents | |
| CN103920469A (en) | Preparation method of citric acid silk adsorbent | |
| Chang et al. | Study on adsorption of ammonium and nitrate in wastewater by modified biochar | |
| CN110252247A (en) | A kind of spherical shape microballon shape walnut shell Quito hole carbon adsorbing material and its preparation method and application | |
| CN106673105A (en) | Nitrogen and phosphorus removal composite filler based on shale and agricultural waste, and preparation method and application thereof | |
| CN103301811A (en) | preparation method of biomass charcoal adsorbent and method for treating oily wastewater by biomass charcoal adsorbent | |
| Kumar et al. | Recovery of nutrients from wastewater by struvite crystallization | |
| CN107265552B (en) | The method of Cr VI in magnetic cellulose/polyglutamic acid coupling material removal waste water | |
| CN109499531A (en) | A kind of adsorbent material for sanitary sewage disposal, preparation method and applications | |
| CN115999506A (en) | Magnesium modified pig manure biochar and application thereof in recycling nitrogen and phosphorus in pig wastewater | |
| CN104275160B (en) | The preparation method of Eucalyptus-calcium chloride compound adsorbent | |
| CN105174354A (en) | Method for removing dye from wastewater by means of edible fungus waste | |
| CN103506081B (en) | The preparation method of a kind of ramee/expanded graphite composite fibre sorbing material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Mo Lingyun Inventor after: Zhu Yinian Inventor after: Zhu Zongqiang Inventor after: Huang Bin Inventor after: Deng Huan Inventor after: Wei Caichun Inventor after: Zhao Xin Inventor before: Zhu Yinian Inventor before: Zhu Zongqiang Inventor before: Huang Bin Inventor before: Deng Huan Inventor before: Wei Caichun Inventor before: Zhao Xin |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |