CN101993101A - Preparation and application of layered double hydroxides with diethylenetriaminepentaacetic acid intercalation - Google Patents
Preparation and application of layered double hydroxides with diethylenetriaminepentaacetic acid intercalation Download PDFInfo
- Publication number
- CN101993101A CN101993101A CN2010105076297A CN201010507629A CN101993101A CN 101993101 A CN101993101 A CN 101993101A CN 2010105076297 A CN2010105076297 A CN 2010105076297A CN 201010507629 A CN201010507629 A CN 201010507629A CN 101993101 A CN101993101 A CN 101993101A
- Authority
- CN
- China
- Prior art keywords
- dtpa
- solution
- diethylene triamine
- pentacetic acid
- triamine pentacetic
- 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
Images
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a preparation method of layered double hydroxides (LDHs) with diethylenetriaminepentaacetic acid (DTPA) intercalation, wherein, Mg-Al LDH is taken as a matrix, and DTPA is introduced into positive charge of a layer balance Mg-Al LDH laminate panel by a coprecipitation method. The preparation method comprises the following steps: dissolving magnesium chloride hexahydrate and aluminum chloride hexahydrate into water to obtain solution A; dissolving the DTPA into ammonia water to obtain solution B; diluting ammonia water with water to obtain solution C; mixing and stirring the three types of solution, keeping standing and aging; and washing and filtering the obtained mixed solution, collecting a gel filter cake, drying the filter cake at constant temperature, and grinding to obtain the product, wherein, the product can be used as a heavy metal adsorbing material. The invention has the advantages that the adsorbing material contains a large quantity of active functional groups, thus having good adsorbing effect; the adsorbing material can obtain better effect with less consumption when in use and has low cost and no pollution; and the adsorbing material is mainly applied to repairing a heavy metal polluted water body and has obvious effect on combined pollution caused by a plurality of heavy metal elements such as lead, cadmium and the like.
Description
Technical field
The present invention relates to the technology of preparing of heavy metal sorbing material, particularly a kind of preparation method of diethylene triamine pentacetic acid (DTPA) intercalation layered double hydroxide and as the application of heavy metal sorbing material.
Background technology
Heavy metal generally extensively is present in occurring in nature with natural concentration, and along with the development of industrial and agricultural production, plurality of heavy metal is discharged in the environment.According to incompletely statistics, the whole world is discharged about 1.5 ten thousand tons of mercury, about 3,400,000 tons of copper, about 5,000,000 tons of lead, about 1,500 ten thousand tons of manganese, about 1,000,000 tons of nickel etc. every year on average at present, and the heavy metal concentration that makes a lot of zones is apparently higher than background value.Heavy metal can not be circulated and participate in food chain often by biological degradation after entering environment, and finally accumulation in vivo, destroys the normal physiological Metabolic activity of organism, and then is detrimental to health.What the heavy metal ions in wastewater treatment process was commonly used has: 1) chemical precipitation method, 2) absorption method, 3) air supporting method, 4) oxidation reduction process, 5) ion exchange method, 6) membrane separation process etc.Be most widely used with chemical precipitation method and absorption method in these methods.
Layered double hydroxide (Layered double hydroxides, LDHs) be a kind of negatively charged ion clay (Anionic Clay) with laminate structure, (Hydrotalcite-like compounds, Htlc), its crystalline structure is identical with hydrotalcite to claim houghite again.The basic structure layer is by M
II-OH and M
IIIThe octahedra composition of-OH because M
2+By M
3+Replace, laminate has positive charge, the pH of this electric charge that is produced by crystalline structure itself and ambient conditions such as dispersion medium, ionogen etc. have nothing to do, and are called permanent positive charge or structure charge.Positive charge superfluous on the laminate comes balance by interlayer anion.Layered double hydroxide (LDHs) interlayer anion has certain transport property and very strong interchangeability, and the negatively charged ion that promptly is between the structural sheet can be by other the inorganic or organic anion exchange in the environment.Layered double hydroxide (LDHs) is to have the structure positive charge and a class material than bigger serface is arranged, and therefore absorption property is preferably arranged.The LDHs of unmodified can be by electronegative material in surface adsorption or the interlayer anion exchange planar water, as Cl
-, I
-Deng halide-ions, PO
4 3-, CrO
4 2-, AsO
2 -, AsO
4 3-, ClO
3 -, SeO
3 2-Deng inorganic oxygen-containing acid ion and organism such as soil ulmin, agricultural chemicals.Yet LDHs is relative less with the research that GOLD FROM PLATING SOLUTION belongs to cation sites in research.
(Diethylenetriaminepenlaacetic Acid DTPA) is clear crystal to diethylene triamine pentacetic acid (DTPA), and is slightly water-soluble, mainly as transition metal and heavy metal ion chelating agent, and is that sequestering power is the strongest in the sequestrant.But discover that diethylene triamine pentacetic acid (DTPA) (DTPA) can suppress the growth of plant, its biomass is reduced, chlorophyll content descends, and has reduced the root system vigor of plant simultaneously, has certain risk and harm so use separately.
Summary of the invention
The objective of the invention is at above-mentioned existing problems, provide that a kind of technology is simple, cost is low, the preparation method of applied widely, non-secondary pollution and diethylene triamine pentacetic acid (DTPA) intercalation layered double hydroxide safe in utilization and as the application of heavy metal sorbing material.
Technical scheme of the present invention:
A kind of preparation method of diethylene triamine pentacetic acid (DTPA) intercalation layered double hydroxide is a matrix with Mg-AlLDH, adopts coprecipitation method that diethylene triamine pentacetic acid (DTPA) DTPA is introduced interlayer balance Mg-AlLDH laminate positive charge, and its preparation process is as follows:
1) with magnesium chloride hexahydrate MgCl
26H
2O and Aluminum Chloride Hexahydrate AlCl
36H
2O is dissolved in the deionized water, makes solution A;
2) diethylene triamine pentacetic acid (DTPA) being dissolved in weight percent concentration is that mixing is evenly made solution B in 25% the ammoniacal liquor;
3) be that 25% ammoniacal liquor is made solution C after with the deionized water dilution with weight percent concentration;
4) under the intense agitation, solution B and solution C added simultaneously make mixed solution in the solution A, mixed solution was stirred after 20 minutes still aging 60 minutes;
5) above-mentioned mixing solutions is transferred in the funnel, to remove excessive ammonia, the gel filter cake in the collection funnel is to container with deionized water rinsing, suction filtration;
6) the above-mentioned container that fills gel being placed baking oven, is 80 ℃ of following constant temperature 24 hours in temperature;
7) gel is taken out, 65 ℃ of oven dry promptly obtain diethylene triamine pentacetic acid (DTPA) intercalation layered double hydroxide (Mg-Al-DTPA LDH) after the grinding.
Total salt concentration is 0.5mol/L in the described solution A, and wherein the ratio of Mg/Al mole number is 2: 1.
Diethylene triamine pentacetic acid (DTPA) DTPA and weight percent concentration are that the ratio of the mole number of 25% ammoniacal liquor is 1: 6 in the described solution B.
Weight percent concentration is 25% ammoniacal liquor and ratio with the volume of deionized water is 1: 4 in the described solution C.
Diethylene triamine pentacetic acid (DTPA) DTPA is 0.0825: 1 with the ratio of total salt concentration mole number in the described mixed solution; Weight percent concentration is 25% ammoniacal liquor and the ratio of total salt concentration mole number is 2.8: 1.
A kind of diethylene triamine pentacetic acid (DTPA) intercalation layered double hydroxide of preparation is as described used as the heavy metal sorbing material.
The chemical equation that the present invention prepares diethylene triamine pentacetic acid (DTPA) intercalation layered double hydroxide is: 0.67Mg
2++ 0.33Al
3++ 0.066DTPA
5-+ 2OH
-→ Mg
0.67Al
0.33(OH)
2(DTPA)
0.066
The present invention has following advantage: 1) advantages of good adsorption effect: the heavy metal sorbing material Mg-Al-DTPA LDH of the present invention's preparation, contain a large amount of activity functional groups, can be by surface complexations such as chemisorption reaction absorption heavy metal, through evidence Mg-Al-DTPA LDH lead had adsorption effect preferably, 2) few, the easy popularization of consumption: this sorbing material can be obtained effect preferably under the less situation of dosage, cost is lower, can not produce secondary pollution, is easily accepted by society; 3) applied widely: this sorbing material is mainly used in the reparation of heavy metal-polluted water, for the combined pollution that is caused by various heavy elements such as plumbous cadmiums significant effect is arranged also, and using method is simple simultaneously, can large-scale promotion application.
Description of drawings
Fig. 1 is the structural representation of Mg-Al-DTPA LDH.
Fig. 2 is Pb
2+Adsorption isothermal line on Mg-Al-DTPA LDH.
Fig. 3 is Pb
2+Kinetics of adsorption on Mg-Al-DTPA LDH.
Fig. 4 is Mg-Al-DTPA LDH absorption Pb
2+Surge capability.
Embodiment
The preparation of embodiment 1:Mg-Al-DTPA LDH
Take by weighing 135.63g MgCl
26H
2O and 80.48g AlCl
36H
2Be dissolved under the O, agitation condition in the 2000ml deionized water; Take by weighing 32.45g DTPA, adding 37ml weight percent concentration is 25% ammonia soln, and mixing is standby; Measure 210ml 25% ammoniacal liquor, adding 840ml deionized water dilution back is standby; Under the intense agitation, the DTPA solution that configured and ammonia soln are added mixing salt solution, vigorous stirring after 20 minutes still aging again 60 minutes; Mixing solutions is transferred in the B, with deionized water wash repeatedly and suction filtration 8 times to remove excessive ammonia, the gel filter cake is to wide-necked bottle in the collection B, place 80 ℃ of baking oven constant temperature, after 24 hours gel in the wide-necked bottle is taken out, 65 ℃ of oven dry promptly obtain diethylene triamine pentacetic acid (DTPA) intercalation layered double hydroxide Mg-Al-DTPA LDH after the grinding.
Embodiment 2:Mg-Al-DTPA LDH adsorption aqueous solution Pb
2+Application
Dispose a series of different Pb
2+The solution of concentration is measured 50ml respectively and is placed the 100ml centrifuge tube as working fluid, takes by weighing Mg-Al-DTPA LDH0.05g and adds respectively and added Pb
2+Pollute in the centrifuge tube of working fluid, Mg-Al-DTPA LDH and soiling solution are than 1g/L, and isothermal vibration 12h gets supernatant liquid behind the high speed centrifugation, with Pb in the atomic absorption spectrophotometer solution
2+Concentration is according to Pb in the working fluid
2+Concentration difference is calculated the adsorptive capacity of Mg-Al-DTPA LDH before and after the concentration.
The result shows: Mg-Al-DTPA LDH pollutes Pb in the solution and has the good adsorption effect, as shown in Figure 2, its adsorption isothermal line accords with Freundlich adsorption isothermal line, its saturated extent of adsorption is about Pb 160mg/g.
Mg-Al-DTPA LDH adsorbs Pb
2+Dynamic experiment:
Compound concentration is 200mg/l Pb respectively
2+Solution solution 500ml is transferred in the 1000ml beaker, Mg-Al-DTPA LDH is set is 1g/L with the solution ratio, and the Mg-Al-DTPALDH 0.5g and the timing that add accurate weighing under the intense agitation respectively begin, and measure Pb after difference is taken a sample membrane filtration constantly
2+Concentration is calculated adsorptive capacity, drawing time and adsorptive capacity relation.
As shown in Figure 3, Mg-Al-DTPALDH and Pb
2+Be swift in response in solution, promptly reach balance in the 200min, the time of response is extremely short.
Mg-Al-DTPA LDH adsorbs Pb
2+The surge capability experiment:
Dispose series of identical Pb
2+Concentration, the solution of different initial pH value are measured 50ml respectively and are placed the 100ml centrifuge tube as working fluid, take by weighing Mg-Al-DTPA LDH 0.05g and add respectively and added Pb
2+Pollute in the centrifuge tube of working fluid, Mg-Al-DTPA LDH and soiling solution are than 1g/L, and isothermal vibration 12h gets supernatant liquid behind the high speed centrifugation, with Pb in the atomic absorption spectrophotometer solution
2+Concentration is according to Pb in the working fluid
2+Concentration difference is calculated the adsorptive capacity of Mg-Al-DTPA LDH before and after the concentration.
As shown in Figure 4, Mg-Al-DTPALDH has stronger surge capability, adsorptive capacity no significant difference under the condition of different pH.
Claims (6)
1. the preparation method of a diethylene triamine pentacetic acid (DTPA) intercalation layered double hydroxide, it is characterized in that: with Mg-Al LDH is matrix, adopt coprecipitation method that diethylene triamine pentacetic acid (DTPA) DTPA is introduced interlayer balance Mg-Al LDH laminate positive charge, preparation process is as follows:
1) with magnesium chloride hexahydrate MgCl
26H
2O and Aluminum Chloride Hexahydrate AlCl
36H
2O is dissolved in the deionized water, makes solution A;
2) diethylene triamine pentacetic acid (DTPA) being dissolved in weight percent concentration is that mixing is evenly made solution B in 25% the ammoniacal liquor;
3) be that 25% ammoniacal liquor is made solution C after with the deionized water dilution with weight percent concentration;
4) under the intense agitation, solution B and solution C added simultaneously make mixed solution in the solution A, mixed solution was stirred after 20 minutes still aging 60 minutes;
5) above-mentioned mixing solutions is transferred in the funnel, to remove excessive ammonia, the gel filter cake in the collection funnel is to container with deionized water rinsing, suction filtration;
6) the above-mentioned container that fills gel being placed baking oven, is 80 ℃ of following constant temperature 24 hours in temperature;
7) gel is taken out, 65 ℃ of oven dry promptly obtain diethylene triamine pentacetic acid (DTPA) intercalation layered double hydroxide (Mg-Al-DTPA LDH) after the grinding.
2. according to the preparation method of the described diethylene triamine pentacetic acid (DTPA) intercalation of claim 1 layered double hydroxide, it is characterized in that: total salt concentration is 0.5mol/L in the described solution A, and wherein the ratio of Mg/Al mole number is 2: 1.
3. according to the preparation method of the described diethylene triamine pentacetic acid (DTPA) intercalation of claim 1 layered double hydroxide, it is characterized in that: diethylene triamine pentacetic acid (DTPA) DTPA and weight percent concentration are that the ratio of the mole number of 25% ammoniacal liquor is 1: 6 in the described solution B.
4. according to the preparation method of the described diethylene triamine pentacetic acid (DTPA) intercalation of claim 1 layered double hydroxide, it is characterized in that: weight percent concentration is 25% ammoniacal liquor and ratio with the volume of deionized water is 1: 4 in the described solution C.
5. according to the preparation method of the described diethylene triamine pentacetic acid (DTPA) intercalation of claim 1 layered double hydroxide, it is characterized in that: diethylene triamine pentacetic acid (DTPA) DTPA is 0.0825: 1 with the ratio of total salt concentration mole number in the described mixed solution; Weight percent concentration is 25% ammoniacal liquor and the ratio of total salt concentration mole number is 2.8: 1.
6. a diethylene triamine pentacetic acid (DTPA) intercalation layered double hydroxide for preparing according to claim 1 is characterized in that: use as the heavy metal sorbing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105076297A CN101993101A (en) | 2010-10-15 | 2010-10-15 | Preparation and application of layered double hydroxides with diethylenetriaminepentaacetic acid intercalation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105076297A CN101993101A (en) | 2010-10-15 | 2010-10-15 | Preparation and application of layered double hydroxides with diethylenetriaminepentaacetic acid intercalation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101993101A true CN101993101A (en) | 2011-03-30 |
Family
ID=43783938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105076297A Pending CN101993101A (en) | 2010-10-15 | 2010-10-15 | Preparation and application of layered double hydroxides with diethylenetriaminepentaacetic acid intercalation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101993101A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302926A (en) * | 2011-06-21 | 2012-01-04 | 长治学院 | Composite modified layered double-metal hydroxide and method for preparing same |
| CN102583631A (en) * | 2012-03-02 | 2012-07-18 | 北京化工大学 | Method of adopting laminar duplex-metal hydroxide to recycle heavy metal ions in sewage |
| CN105148846A (en) * | 2015-07-20 | 2015-12-16 | 农业部环境保护科研监测所 | DTPA modified material and preparation method for rapid-full-dissociation type DGT (Diffusive gradients in thin films) coupling phase prepared therefrom |
| CN105236456A (en) * | 2014-07-10 | 2016-01-13 | 商丘师范学院 | Preparation and application for 3,3'-dithiodipropionic acidintercalated layered double metal hydroxide |
| CN110215895A (en) * | 2019-07-16 | 2019-09-10 | 福州大学 | A kind of organic anion intercalation modifying magnalium laminar double-hydroxide adsorbent |
| CN111052909A (en) * | 2020-01-19 | 2020-04-24 | 四川省天晟源环保股份有限公司 | Safe passivation and planting method for heavy metal cadmium in rice field |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827702A (en) * | 2006-02-22 | 2006-09-06 | 北京化工大学 | Conductive polymer-intercalated hydrotalcite and method for preparing same |
| CN101544815A (en) * | 2009-04-14 | 2009-09-30 | 桂林工学院 | A preparing method for unsaturated polyester resins flame-retardant composite material |
-
2010
- 2010-10-15 CN CN2010105076297A patent/CN101993101A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827702A (en) * | 2006-02-22 | 2006-09-06 | 北京化工大学 | Conductive polymer-intercalated hydrotalcite and method for preparing same |
| CN101544815A (en) * | 2009-04-14 | 2009-09-30 | 桂林工学院 | A preparing method for unsaturated polyester resins flame-retardant composite material |
Non-Patent Citations (2)
| Title |
|---|
| XUEFENG LIANG等: "Sorption of lead ion by layered double hydroxide intercalated with diethylenetriaminepentaacetic acid", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》 * |
| XUEFENG LIANG等: "Sorption of lead ion by layered double hydroxide intercalated with diethylenetriaminepentaacetic acid", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》, vol. 366, 16 May 2010 (2010-05-16) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302926A (en) * | 2011-06-21 | 2012-01-04 | 长治学院 | Composite modified layered double-metal hydroxide and method for preparing same |
| CN102583631A (en) * | 2012-03-02 | 2012-07-18 | 北京化工大学 | Method of adopting laminar duplex-metal hydroxide to recycle heavy metal ions in sewage |
| CN102583631B (en) * | 2012-03-02 | 2013-10-30 | 北京化工大学 | Method of adopting laminar duplex-metal hydroxide to recycle heavy metal ions in sewage |
| CN105236456A (en) * | 2014-07-10 | 2016-01-13 | 商丘师范学院 | Preparation and application for 3,3'-dithiodipropionic acidintercalated layered double metal hydroxide |
| CN105148846A (en) * | 2015-07-20 | 2015-12-16 | 农业部环境保护科研监测所 | DTPA modified material and preparation method for rapid-full-dissociation type DGT (Diffusive gradients in thin films) coupling phase prepared therefrom |
| CN105148846B (en) * | 2015-07-20 | 2017-09-01 | 农业部环境保护科研监测所 | A kind of DTPA it is material modified and its prepare the release DGT combinations phase preparation method of quick complete solution |
| CN110215895A (en) * | 2019-07-16 | 2019-09-10 | 福州大学 | A kind of organic anion intercalation modifying magnalium laminar double-hydroxide adsorbent |
| CN111052909A (en) * | 2020-01-19 | 2020-04-24 | 四川省天晟源环保股份有限公司 | Safe passivation and planting method for heavy metal cadmium in rice field |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101993101A (en) | Preparation and application of layered double hydroxides with diethylenetriaminepentaacetic acid intercalation | |
| CN105293603B (en) | A kind of heavy metal-polluted water treatment agent and its processing method | |
| CN105060579B (en) | A kind of method of advanced treating fluoride waste | |
| CN109289790B (en) | Preparation method of multifunctional composite hydrogel | |
| CN102001766B (en) | Defluorinating method of photovoltaic wastewater | |
| CN103523969B (en) | Special apparatus for removing heavy metal ions in wastewater, and method thereof | |
| CN102732731B (en) | Method for extracting valuable metals and refining zinc sulphate monohydrate from zinc-containing waste material | |
| CN105126742A (en) | Method for treating fluorine-containing wastewater by using modified kaolin adsorbent | |
| CN102583631A (en) | Method of adopting laminar duplex-metal hydroxide to recycle heavy metal ions in sewage | |
| CN102464810A (en) | Hydroxyapatite-chitosan (HA-CTS) composite material for treating waste water and preparation method thereof | |
| CN101973619B (en) | Method for treating waste water from copper smelting by using modified ardealite | |
| CN102531233A (en) | Heavy-metal-containing electroplating wastewater treatment and heavy metal recycling method | |
| CN104475039B (en) | A kind of remove fluorine in wastewater, the biological adsorption agent of heavy metal and methods for making and using same thereof | |
| CN109647351B (en) | Bagasse loaded iron hydroxide adsorbent and preparation method and application thereof | |
| JP5754769B2 (en) | Aggregation method | |
| CN110252254A (en) | A kind of pair of cadmium ion has modification houghite and its application of strong suction-operated | |
| CN110255562B (en) | Activated carbon washing system and washing process | |
| CN205773743U (en) | A kind of boiler acid washing wastewater processing system | |
| CN107686192A (en) | A kind of phosphorous and Ammonia-nitrogen wastewater treatment technology | |
| CN1273397C (en) | Waste water treatment process in fluorobenzene production | |
| CN113559820A (en) | Preparation method, application and recovery method of phosphorus removal adsorbent for fosfomycin pharmaceutical wastewater | |
| CN103449628B (en) | Deep dehydration sludge water is utilized to remove the method for phosphorus in thickening sludge water | |
| CN105330000B (en) | A kind of processing method of phosphoric acid waste water | |
| CN101948220A (en) | Method for treating printing and dyeing wastewater | |
| CN109608020A (en) | A kind of composite flocculation agent and preparation method thereof for Treatment of Sludge |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110330 |