CN103736463B - Modification method and application of metal adsorbent containing persimmon tannin - Google Patents
Modification method and application of metal adsorbent containing persimmon tannin Download PDFInfo
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- CN103736463B CN103736463B CN201410006461.XA CN201410006461A CN103736463B CN 103736463 B CN103736463 B CN 103736463B CN 201410006461 A CN201410006461 A CN 201410006461A CN 103736463 B CN103736463 B CN 103736463B
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Abstract
The invention belongs to the technical field of heavy metal wastewater treatment, and in particular relates to a modification treatment method of a metal adsorbent containing persimmon tannin and an application of the metal adsorbent containing persimmon tannin to heavy metal ion adsorption. The method comprises the following steps: (1) cleaning persimmon fruits or persimmon peels, smashing, performing high-pressure leaching by adding water, and concentrating and drying so as to obtain persimmon powder; (2) mixing the persimmon powder with a dilute sodium hydroxide solution, fully stirring, then adding an aldehyde solution, fully reacting, then washing with dilute nitric acid and water until obtaining a neutral mixture, removing soluble substances, drying and smashing so as to obtain the metal adsorbent; and (3) adding the metal adsorbent into an alkali solution, fully reacting at 60 DEG C under the protection of N2, then washing the metal adsorbent with the water to be neutral, removing the soluble substances, drying and smashing so as to obtain the alkali-modified metal adsorbent containing the persimmon tannin. According to the method, the alkali-modified metal adsorbent containing the persimmon tannin is modified by the alkali, so that the adsorption capacity of the metal adsorbent to precious and heavy metal ions is obviously improved; particularly, the treatment capacity of the metal adsorbent to wastewater containing multiple heavy metal ions is greatly improved.
Description
Technical field
The invention belongs to technical field of heavy metal wastewater treatment, be specifically related to a kind of containing the method for modifying of persimmon tannin metal absorbent and the adsorption applications of heavy metal ion.
Background technology
China is the country of origin of persimmon (Diospyros kaki Thunb.), is also that persimmon production history is the longest, area is maximum in the world (about 660,000 hectares; Account for the world 90%) and output the highest (3,260,000 tons; Account for the world 76%) country.The tradition producing region overwhelming majority is puckery persimmon, and is distributed in Around the house and the edge of a field more, to gather inconvenience as commodity fresh fruit; And persimmon becomes to spend easily, and young fruit period (period that persimmon tannin content is the highest) physiological fallen fruit is more, these physiological fallen fruits and the sick wormed fruit, malformed fruit etc. that manually remove not only a considerable number of, and almost nil cost; In addition, China about 50% astringent persimmon fruit is practically applicable to make dried persimmon, and consequent discarded persimmon skin accounts for fresh fruit weight 10%.Persimmon fruit and pericarp thereof are rich in persimmon tannin (proanthocyanidin, belong to condensed tannin), the B ring of persimmon tannin molecule contains a large amount of ortho position phenolic hydroxyl groups, can stable chelate be formed with metal ion generation complexation reaction or redox reaction occur and generate lower valency ion or zero-valent state metal, utilize this characteristic to carry out metallic element recovery and reuse.It is raw material that author utilizes persimmon young fruit period naturally to come off with the young fruit manually removed in previous work, and formaldehyde is crosslinking agent, has prepared one containing persimmon tannin metal absorbent, and finds Au in its energy efficient adsorption aqueous solution
3+(the patent No.: ZL201110030839.6; Xie et al., 2013), Pd
2+(patent No.: ZL201110030830.5), Cu
2+and Pb
2+(patent No.: ZL201110030817.X).But this adsorbent exists containing the not high defect of contents of many kinds of heavy metal ion waste treatment capacity, especially to periodic table of elements S p-block element p metal ion as Mg
2+with Ca
2+adsorption effect undesirable.Owing to often containing contents of many kinds of heavy metal ion composition in actual heavy metal-containing waste water, therefore, exploitation can be necessary by the low-cost sorbent simultaneously processed containing contents of many kinds of heavy metal ion industrial wastewater very much.
Summary of the invention
Object of the present invention is exactly exist containing the limited a kind of method of modifying of contents of many kinds of heavy metal ion waste treatment capacity to overcome the above-mentioned persimmon tannin metal absorbent that contains.This preparation method adopts alkali modification, and modified adsorbent has stronger adsorption capacity to expensive, heavy metal ion, has especially increased substantially the disposal ability containing contents of many kinds of heavy metal ion waste water.
Realize technical scheme of the present invention as described below:
(1) containing the preparation of persimmon tannin persimmon powder:
The raw material persimmon fruit or persimmon skin that contain persimmon tannin are cleaned up, pulverize, according to mass/volume ratio (g/mL) for 1:5-20 adds water, lixiviate 5-30min under 121 DEG C of high pressure, leaching liquor concentrates through rotary evaporation, and concentrate obtains containing persimmon tannin persimmon powder after vacuum freeze drying 24-72h.
(2) containing the preparation of persimmon tannin metal absorbent:
What (1) step obtained adds in there-necked flask containing persimmon tannin persimmon powder, by mass/volume ratio (g/mL) for 1:2-5 adds 0.1-0.5mol/L NaOH solution, after fully stirring again by mass/volume ratio (g/mL) for 5-10:1 adds aldehyde solution, at N
2after the lower fully reaction of protection, use a large amount of 0.01-0.1mol/L HNO respectively
3solution and deionized water are washed to neutrality and are removed solable matter, pulverize after vacuum freeze drying, namely obtain containing persimmon tannin metal absorbent.
(3) containing the modification of persimmon tannin metal absorbent:
The metal obtained with (2) step contains persimmon tannin metal absorbent for raw material, by mass/volume ratio (g/mL) for 1:10-100 adds aqueous slkali, N
2stir 4-24h at protecting 40-80 DEG C, the centrifugal 10min of 5000g, removing supernatant, is washed till neutrality by a large amount of deionized water, vacuum freeze drying 24-48h by the modification crude product of gained, namely obtains alkali modification containing persimmon tannin metal absorbent;
Wherein:
Kind containing persimmon tannin raw material in above-mentioned steps (1) is not limit, and high pressure lixiviate pressure is 0.15-0.25MPa, and vacuum freeze drying vacuum is lower than same under 12.0Pa();
In above-mentioned steps (2), aldehyde solution is 37% formalin, 40% acetaldehyde solution or 25% glutaraldehyde water solution.
In above-mentioned steps (3), aqueous slkali is NaOH or KOH solution, and concentration is 0.1-1.0mol/L; Mixing speed is 150-500r/min.
Method of the present invention can be applied containing in persimmon tannin modified metal absorbent in preparation, it is also included in the application in absorption and Footwall drift, and the modification obtained especially by said method is widely used in absorption and Footwall drift containing persimmon tannin metal absorbent.
The modification utilizing the present invention to prepare, containing the concrete preparation method of persimmon tannin metal absorbent, has the following advantages:
(1) raw material of the present invention is produced or processing waste from the persimmon such as discarded persimmon fruit, persimmon skin, aboundresources and with low cost.
(2) what prepared by the present invention is easy containing persimmon tannin persimmon powder, preparation method thereof, is applicable to factorial praluction.
(3) the modified adsorbent preparation method for preparing of the present invention is easy, is applicable to factorial praluction.
(4) modified adsorbent prepared of the present invention is very strong to the disposal ability containing contents of many kinds of heavy metal ion waste water, can simultaneously completely adsorption removal containing all heavy metal ion in contents of many kinds of heavy metal ion waste water.
(5) modified adsorbent prepared of the present invention is to Au
3+the stronger reducing power of tool, can by Au in adsorption process
3+be reduced into metallic state gold, and do not need to re-use reducing agent and reduced.
Accompanying drawing explanation
Fig. 1: alkali modification prepared by the present invention is containing the scanning electron microscope (SEM) photograph of persimmon tannin metal absorbent.
Fig. 2: the infrared spectrogram of rear before modified metal absorbent prepared by the present invention.(abscissa: scanning wavelength scope; Ordinate: absorption intensity)
Fig. 3: modified to Cu under variable concentrations NaOH solution containing persimmon tannin metal absorbent
2+and Pb
2+adsorbance.(abscissa: NaOH solution modification concentration; Ordinate: alkali modification contains persimmon tannin metal absorbent to Cu
2+and Pb
2+adsorbance)
Fig. 4: rear before modified alkali modification prepared by the present invention contains persimmon tannin metal absorbent to Cu
2+, Pb
2+and Au
3+adsorption capacity comparison diagram.(abscissa: species of metal ion; Ordinate: contain persimmon tannin metal absorbent before and after alkali modification to Cu
2+, Pb
2+and Au
3+adsorbance)
Fig. 5: alkali modification prepared by the present invention is containing persimmon tannin metal absorbent absorption Au
3+after micro-Electronic Speculum figure (golden yellow object is gold grain).
Detailed description of the invention
Embodiment 1 alkali modification is containing the preparation of persimmon tannin metal absorbent
(1) containing the preparation of persimmon tannin persimmon powder:
Raw material persimmon fruit (kind is ' respectful city seadless kaki fruit ') containing persimmon tannin is cleaned up, pulverize, water is added according to mass volume ratio (g/mL) 1:10, lixiviate 15min under 121 DEG C of high pressure (0.25MPa), leaching liquor concentrates through rotary evaporation, and concentrate obtains containing persimmon tannin persimmon powder after vacuum freeze drying (vacuum is lower than 12.0Pa) 72h.
(2) containing the preparation of persimmon tannin metal absorbent:
The persimmon powder 50g that (1) step obtains is added in there-necked flask, adds the 0.125mol/L NaOH solution of 100mL, after fully stirring, add 10mL37% formalin again, N
2after protecting 60 DEG C of water-bath 4h, use a large amount of 0.05mol/L HNO respectively
3solution and deionized water are washed to neutrality and are removed solable matter, and vacuum freeze drying (vacuum is lower than 12.0Pa) is pulverized afterwards, namely obtains containing persimmon tannin metal absorbent.
(3) containing the modification of persimmon tannin metal absorbent:
The metal absorbent 10g that (2) step obtains is added in there-necked flask, adds 100mL1.0mol/L NaOH solution, N
212h is stirred with the speed of 200r/min at protecting lower 60 DEG C, the centrifugal 10min of 5000g, removing supernatant, a large amount of deionized water of modification crude product is washed till neutrality, vacuum freeze drying (vacuum is lower than 12.0Pa) 48h, namely obtains alkali modification containing persimmon tannin metal absorbent;
Above-mentioned alkali modification process improves heat endurance and the specific area of adsorbent, reduces bulk density (see table 1) simultaneously.
Table 1 is before modified afterwards containing the part physical character of persimmon tannin metal absorbent
The product yield of the present embodiment is about 50%.
Embodiment 2 alkali modification is containing the preparation of persimmon tannin metal absorbent
(1) containing the preparation of persimmon tannin persimmon powder:
Raw material persimmon skin (kind is ' respectful city seadless kaki fruit ') containing persimmon tannin is cleaned up, pulverize, water is added than 1:5 according to mass/volume (g/mL), in 121 DEG C of high pressure (0.25MPa) lixiviate 15min, leaching liquor concentrates through rotary evaporation, and concentrate obtains containing persimmon tannin persimmon powder after vacuum freeze drying 72h.
(2) containing the preparation of persimmon tannin metal absorbent:
The persimmon powder 50g that (1) step obtains is added in there-necked flask, adds the 0.125mol/L NaOH solution of 100mL, add 25% glutaraldehyde water solution of 10mL after fully stirring again, N
2after protecting 60 DEG C of water-bath 8h, use the HNO of a large amount of 0.05mol/L respectively
3solution and deionized water are washed to neutrality and are removed solable matter, and vacuum freeze drying (vacuum is lower than 12.0Pa) is pulverized afterwards, namely obtains containing persimmon tannin metal absorbent.
(3) containing the modification of persimmon tannin metal absorbent:
The metal absorbent 10g that (2) step obtains is added in there-necked flask, adds 500mL0.5mol/L NaOH solution, N
224h is stirred with the speed of 200r/min at protecting lower 40 DEG C; the centrifugal 10min of 5000g, removing supernatant, a large amount of deionized water of modification crude product is washed till neutrality; vacuum freeze drying (vacuum is lower than 12.0Pa) 48h, namely obtains alkali modification containing persimmon tannin metal absorbent.
The product yield of the present embodiment is about 50%.
Embodiment 3 alkali modification is containing the preparation of persimmon tannin metal absorbent
(1) containing the preparation of persimmon tannin persimmon powder:
Raw material persimmon fruit (kind is ' Fuping point persimmon ') containing persimmon tannin is cleaned up, pulverize, water is added according to mass volume ratio (g/mL) 1:10, lixiviate 15min under 121 DEG C of high pressure (0.25MPa), leaching liquor concentrates through rotary evaporation, and concentrate obtains containing persimmon tannin persimmon powder after vacuum freeze drying (vacuum is lower than 12.0Pa) 72h.
(2) containing the preparation of persimmon tannin metal absorbent:
The persimmon powder 50g that (1) step obtains is added in there-necked flask, adds the 0.125mol/L NaOH solution of 100mL, after fully stirring, add 10mL40% acetaldehyde solution again, N
2after protecting 60 DEG C of water-bath 8h, use a large amount of 0.05mol/L HNO respectively
3solution and deionized water are washed to neutrality and are removed solable matter, and vacuum freeze drying (vacuum is lower than 12.0Pa) is pulverized afterwards, namely obtains containing persimmon tannin metal absorbent.
(3) containing the modification of persimmon tannin metal absorbent:
The metal absorbent 10g that (2) step obtains is added in there-necked flask, adds 100mL1.0mol/L KOH solution, N
24h is stirred with the speed of 200r/min at protecting lower 80 DEG C, the centrifugal 10min of 5000g, removing supernatant, a large amount of deionized water of modification crude product is washed till neutrality, vacuum freeze drying (vacuum is lower than 12.0Pa) 48h, namely obtains alkali modification containing persimmon tannin metal absorbent;
The product yield of the present embodiment is about 40%.
Embodiment 4 utilizes alkali modification to contain persimmon tannin metal absorbent to the process containing contents of many kinds of heavy metal ion simulated wastewater
(1) containing the preparation of contents of many kinds of heavy metal ion simulated wastewater: the nitrate (analyzing pure) of each heavy metal is mixed with each heavy metal ion (Ca
2+, Cd
2+, Cu
2+, Fe
3+, Mg
2+, Mn
2+, Pb
2+and Zn
2+) concentration be 0.1mmol/L containing contents of many kinds of heavy metal ion simulated wastewater, and utilize rare HNO
3its pH value is adjusted to 5.0 by solution and dilute NaOH solution.
(2) what adsorbent embodiment 1 obtained was prepared by solid-to-liquid ratio 1g/L and the present embodiment (1) step mix containing contents of many kinds of heavy metal ion simulated wastewater, then in constant temperature oscillator 30 DEG C with 200r/min vibration 24h.
(3) filtration or the centrifugal 10min of 5000g are by Separation of Solid and Liquid, measure each metal ion content (absorption result is in table 2) in the rear solution of absorption with atomic absorption spectrophotometer (AAS) or inductively coupled plasma atomic emission spectrometer (ICP-AES).
Table 2 contains persimmon tannin metal absorbent before modified afterwards to the adsorption effect of coexistent metallic ion
From the result of the test of above-mentioned table 2, alkali modification almost can adsorb containing all heavy metal ion in contents of many kinds of heavy metal ion simulated wastewater containing persimmon tannin metal absorbent simultaneously completely, and it is undesirable to the adsorption effect of contents of many kinds of heavy metal ion before modified.Embodiment 5 utilizes alkali modification to contain persimmon tannin metal absorbent and reclaims gold in waste mobile telephone circuit board
(1) waste mobile telephone circuit board is pulverized (particle diameter < 250 μm), get 3g circuit board powder and be added in digest tube (200mL), then add 50mL chloroazotic acid reaction 12h, after filtration, obtain filtrate.
(2) adsorbent 15mg embodiment 1 prepared mixes with 50mL waste mobile telephone circuit board leaching liquor (by volume diluting 10 times), is placed in constant temperature oscillator, and 30 DEG C with 200r/min vibration 24h.
(3) centrifugal, the concentration of each metal ion in supernatant is measured with atomic absorption spectrophotometer (AAS) or inductively coupled plasma atomic emission spectrometer (ICP-AES).
Absorption Au
3+after by micro-electron microscopic observation to gold grain (see figure 5).
Embodiment 4 and 5 is only utilize alkali modification to contain persimmon tannin metal absorbent to adsorb and 2 specific embodiments in Footwall drift; be noted that for those skilled in the art; under the premise without departing from the principles of the invention; this adsorbent also can be utilized to carry out the application of other metal ionic adsorption aspects, and these application processes also should be considered as the protection domain of this invention.
Leading reference
1.Feng Xie,Zaijun Fan,Qinglin Zhang,Zhengrong Luo.Selective adsorption of Au
3+from aqueous solutions using persimmon powder-formaldehyde resin.Journal of Applied Polymer Science,2013,130:3937-3946.
Claims (3)
1., containing a method of modifying for persimmon tannin metal absorbent, it is characterized in that comprising the following steps:
(1) containing the preparation of persimmon tannin persimmon powder:
The raw material persimmon fruit or persimmon skin that contain persimmon tannin are cleaned up, pulverize, according to mass volume ratio (g/mL) for 1:5-20 adds water lixiviate 5-30min under 121 DEG C of high pressure, leaching liquor concentrates through rotary evaporation, and concentrate obtains containing persimmon tannin persimmon powder after vacuum freeze drying 24-72h;
(2) containing the preparation of persimmon tannin metal absorbent:
The persimmon powder obtained in (1) step is added in there-necked flask, by mass/volume ratio (g/mL) for 1:2-5 adds the NaOH solution of 0.1-0.5mol/L, after abundant stirring again by mass/volume ratio (g/mL) for 5-10:1 adds aldehyde solution, at N
2after the lower fully reaction of protection, use the HNO of 0.01-0.1mol/L respectively
3solution and deionized water are washed to neutrality and are removed solable matter, pulverize after vacuum freeze drying, obtain containing persimmon tannin metal absorbent;
(3) containing the modification of persimmon tannin metal absorbent:
What obtain with (2) step contains persimmon tannin metal absorbent for raw material, by mass/volume ratio (g/mL) for 1:10-100 adds aqueous slkali, at N
2at 40-80 DEG C, stir 4-24h under protection, the centrifugal 10min of 5000g, removing supernatant, obtains modification crude product deionized water and is washed till neutrality, vacuum freeze drying 24-48h, obtains alkali modification containing persimmon tannin metal absorbent;
Wherein:
Kind containing persimmon tannin raw material in step (1) is not limit, and high pressure lixiviate pressure is 0.15-0.25MPa, and vacuum freeze drying vacuum is lower than 12.0Pa;
In step (2), aldehyde solution is the glutaraldehyde water solution of the formalin of 37% concentration, the acetaldehyde solution of 40% concentration or 25% concentration;
In step (3), aqueous slkali is NaOH or KOH solution, and concentration is 0.1-1.0mol/L; Mixing speed is 150-500r/min.
2. method described in claim 1 contains the application in persimmon tannin modified metal absorbent in preparation.
3. application according to claim 2, is included in the application in absorption and Footwall drift.
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| CN105289519A (en) * | 2015-10-19 | 2016-02-03 | 辽宁大学 | Persimmon tannin adsorbent and preparing method and application thereof |
| CN105536713B (en) * | 2015-12-16 | 2018-06-29 | 湖南广播电视大学 | The extraction of jute polysaccharide and its application in hexavalent chromium is removed |
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| CN105478085B (en) * | 2015-12-16 | 2018-06-29 | 湖南广播电视大学 | Using jute as the preparation and application of the adsorbent of raw material |
| CN105800726A (en) * | 2016-06-06 | 2016-07-27 | 中南林业科技大学 | Application of acorn polyphenol extract |
| CN106179241B (en) * | 2016-07-14 | 2018-08-24 | 胡大苇 | A kind of preparation method of the chelating agent of processing heavy metal in waste water |
| CN106268678A (en) * | 2016-09-16 | 2017-01-04 | 佛山市中国地质大学研究院 | A kind of preparation method of modified Rhizoma Dioscoreae Cirrhosae tannin heavy metal absorbent |
| CN106582553A (en) * | 2016-12-05 | 2017-04-26 | 长沙秋点兵信息科技有限公司 | Preparation method of adsorbent for heavy metal waste liquid treatment |
| CN106745453A (en) * | 2016-12-05 | 2017-05-31 | 长沙秋点兵信息科技有限公司 | Treatment method of heavy metal waste liquid |
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