CN110368908A - A kind of polyphenol modification of chitosan adsorbent and preparation method thereof and the application in germanium recycling - Google Patents
A kind of polyphenol modification of chitosan adsorbent and preparation method thereof and the application in germanium recycling Download PDFInfo
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- CN110368908A CN110368908A CN201910669532.7A CN201910669532A CN110368908A CN 110368908 A CN110368908 A CN 110368908A CN 201910669532 A CN201910669532 A CN 201910669532A CN 110368908 A CN110368908 A CN 110368908A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
Abstract
The invention belongs to rare earth recovery technical fields, and in particular to a kind of polyphenol modification of chitosan adsorbent and preparation method thereof and the application in germanium recycling.Preparation method includes the following steps: after being cleaned and dried crab shell, and hydrochloric acid solution is added and impregnates, and is stirred continuously, after impregnating 10~15h, then crab shell washed to neutrality, sodium hydroxide solution is added, it is heated to 80-100 DEG C of reaction 2-6h, neutrality is washed to, is separately added into the KMnO of l%4And NaHSO3Solution is rinsed, dry white solid, chitin；Dry chitin is taken, sodium hydroxide solution is added, 80-120 DEG C of reaction 5-10h obtains white chitosan solid；Polyphenol and chitosan solid are placed in there-necked flask and are added methanol, is stirred continuously to dissolution, 12-24h is stirred at 20-50 DEG C, obtains polyphenol modification of chitosan adsorbent after washing is dry.Polyphenol modification of chitosan adsorbent prepared by the present invention can effectively adsorb germanium ion, energy free consumption, energy conservation and environmental protection, and adsorbent preparation is convenient, and abundance has actual practicability.
Description
Technical field
The invention belongs to dilute scattered recovery technology fields, and in particular to a kind of polyphenol modification of chitosan adsorbent and its preparation side
Method and the application in germanium recycling, this adsorbent can the effectively germanium metallic elements from solution.
Background technique
Germanium (Ge) member procatarxis is all relatively low in the reserves of nature, and normal association is in other metals or mineral, substantially without solely
Vertical mineral exist, and referred to as rare and scatter element.The seventies rise, and the consumption market of world's germanium is from single semiconductor field
Expand to the fields such as infrared, optical fiber, catalyst, for example, using germanium metal in the refraction coefficient of certain range of wavelengths be it is constant,
With the image-forming block such as window, lens, optical filter etc. of germanium production infrared laser, thermal imaging system, infrared radiation thermometer etc..Germanium is also made
It is used in optical fiber for ideal dopant, for improving the refractive index of fibre core.There is peace with the PET resin that germanium makees catalyst
The advantages that Atoxic, air-tightness are good；Germanium can make thermoelectric material, for manufacturing solar battery.It is a variety of in recent years that there is biology
Active organic germanium compounds are widely used in medicine and field of biology.With the high speed development of science and technology, germanium is by increasingly
More is applied in high-tech industry, and the consumption of germanium is growing day by day, and domestic and international germanium resource shortcoming, supply falls short of demand, therefore germanium has
Effect is extracted and is recycled increasingly important.
The recovery technology of germanium has: the acid-hatching of young eggs, including the normal pressure acid-hatching of young eggs and pressurized acid leaching method, and germanium is extracted from zinc concentrate, is obtained
Very high leaching rate is obtained, but since the consumption of acid is big, environmental pollution is serious, there are also certain difficulties for producing；Alkali leaching
Method, decomposing leached mud with caustic soda makes germanium enter solution, by solvent extraction Ti recovery, handles zinc leaching residue, behaviour by alkaline leaching
Make simply, alkali is also renewable to return use, but when alkali concentration is higher in leachate, it is more difficult to will cause solid-liquor separation；Extraction, though
It has been industrialized that, but there is the problems such as easily emulsification, scavenging solution oil content is high and traditional chlorization distillation method extraction germanium loss rate
The problems such as height, zinc dust precipitation technique generates hypertoxic gas arsenic hydride；Active carbon adsorption, active carbon have highly developed gap
Structure and high specific surface area, renewable reuse, but cannot effectively remove some inorganic cations.
Biological adsorption material of the chitosan as natural green, the metal active site with amido and methylol, itself
Chelation can occur with various metals ion, there is wider application value and application field；And the change of chitosan
It is extensive to learn method of modifying, graft copolymerization can be carried out；It is crosslinked by the aldehyde or acid anhydrides bifunctional etc. of chitosan,
Make it insoluble in diluted acid after crosslinking, property is stablized.How chitosan is modified, it is made to have adsorption capacity to germanium, at present also
There is not related article to report it.
Summary of the invention
In view of the problems of the existing technology, it is an object of the invention to rationally using discarded crab shell, select discarded river
Crab shell is raw material, extracts chitosan by a series of experiments, is simply modified for adsorbing germanium with polyphenol.Operation side of the invention
Method is simple, resourceful, pollution-free.For the functionalization chitosan absorbent prepared to the large amount of adsorption of germanium, selectivity is high, is applicable in
Extensively, there is practical application.
The present invention is achieved through the following technical solutions: a kind of polyphenol modification of chitosan adsorbent, preparation method include
Following steps:
1) after being cleaned and dried crab shell, hydrochloric acid solution is added and impregnates, and is stirred continuously, after impregnating 10~15h, then by crab shell
Washing is added sodium hydroxide solution, is heated to 80-100 DEG C of reaction 2-6h, is washed to neutrality, is separately added into l%'s to neutrality
KMnO4And NaHSO3Solution is rinsed, dry white solid, chitin；
2) dry chitin is taken, sodium hydroxide solution is added, 80-120 DEG C of reaction 5-10h obtains white chitosan solid；
3) polyphenol and chitosan solid are placed in there-necked flask and are added methanol, be stirred continuously to dissolution, at 20-50 DEG C
12-24h is stirred, obtains polyphenol modification of chitosan adsorbent after washing is dry.
Preferably, above-mentioned a kind of polyphenol modification of chitosan adsorbent, in step 1), by solid-to-liquid ratio, crab shell: hydrochloric acid=
1g:10mL-20mL；The mass concentration of the hydrochloric acid is 2%~6%；By solid-to-liquid ratio, crab shell: sodium hydroxide=1g:10mL-
20mL；The mass concentration of the sodium hydroxide is 8%~10%.
Preferably, above-mentioned a kind of polyphenol modification of chitosan adsorbent, in step 2), by solid-to-liquid ratio, chitin: hydroxide
Sodium=1g:10mL-30mL；The mass concentration of the sodium hydroxide solution is 40%~50%.
Preferably, above-mentioned a kind of polyphenol modification of chitosan adsorbent, polyphenol described in step 3) are 2,3,4- tri- hydroxyls
One of benzaldehyde, 3,4- 4-dihydroxy benzaldehyde, 4- hydroxy benzaldehyde.
Preferably, above-mentioned a kind of polyphenol modification of chitosan adsorbent, in step 3), in mass ratio, polyphenol: chitosan=
1:1-5.
Preferably, above-mentioned a kind of polyphenol modification of chitosan adsorbent, in step 3), by solid-to-liquid ratio chitosan: methanol=
1g:40mL-80mL.
Application of the above-mentioned polyphenol modification of chitosan adsorbent in recycling rare and scatter element.
Preferably, above-mentioned application, the rare and scatter element are germanium.
Preferably, above-mentioned application, in the solution of Yu Hanyou Germanium, the pH for adjusting solution is 1-6, and above-mentioned polyphenol is added
Modification of chitosan adsorbent, at 20-50 DEG C, oscillation rate is after concussion absorption 5-24h, to use eluant, eluent under 150~200r/min
Elution, the eluant, eluent is the NaOH solution that concentration is 3-10%.
Preferably, above-mentioned application, by solid-to-liquid ratio, polyphenol modification of chitosan adsorbent: the solution containing rare earth element=
1mg:1mL；The concentration containing rare and scatter element solution is 10mg L-1-100mg L-1。
The invention has the following advantages:
1. the polyphenol modification of chitosan adsorbent that the present invention prepares is by the amino and polyphenol on the surface of chitosan
Aldehyde radical reaction introduce hydroxyl and obtain, separation and concentration is high-efficient, can be from the molten of the foreign ions intermediate ions such as Co (II), Ni (II)
Selective absorption germanium in liquid.Method energy conservation and environmental protection of the invention, preparation are simple, short preparation period, and cheap and source is rich
Richness has practical application.
2. abundant raw material: China discard crab shell amount it is very big, so raw material facilitate acquisition and it is low in cost, be suitable for industry
Change application.
3. easy to operate: the present invention is carried out by the aldehyde radical of simple chemical treatment method polyphenol and the amino of chitosan
Condensation, synthesis process are simple and fast and safe.
4. pollution-free: the equal nonhazardous of solvent used in the method for the present invention, no discharging of waste liquid, therefore environment can't be produced
Raw pollution.
5. in the invention, under certain acidity, composite material has biggish adsorbance to the germanium in waste liquid, and uses 3%
NaOH can elute the germanium of absorption.
6. polyphenol modification of chitosan adsorbent obtained by the invention can be from the cobalt of high concentration, the practical mixing of the simulation of nickel
Selective absorption germanium in solution is expected to the Ti recovery in practical feed liquid.
In conclusion polyphenol modification of chitosan adsorbent prepared by the present invention can effectively adsorb germanium ion, energy free
Consumption, energy conservation and environmental protection, and also adsorbent preparation is convenient, and abundance has actual practicability.
Detailed description of the invention
Fig. 1 is polyphenol modification of chitosan adsorbent preparation process
Fig. 2 be embodiment 1 prepare polyphenol modification of chitosan adsorbent infrared figure (a:THB-CS, b:HBD-CS, c:
PTD-CS、d:CS)
Fig. 3 is the scanning figure (A:CS, B:THB-CS) of polyphenol modification of chitosan adsorbent prepared by embodiment 1
Fig. 4 be embodiment 1 prepare polyphenol modification of chitosan adsorbent under different acidity to the adsorption effect of germanium
Fig. 5 is the infrared figure before and after polyphenol modification of chitosan adsorbent THB-CS absorption Ge (IV) prepared by embodiment 1
Fig. 6 be embodiment 1 prepare polyphenol modification of chitosan adsorbent with arsenic, nickel, lead, cobalt, iron, zinc, manganese plasma
To the separating effect statistical chart of germanium in the solution coexisted
Specific embodiment
The preparation of 1 polyphenol modification of chitosan adsorbent of embodiment
(1) preparation of 2,3,4- tri hydroxybenzaldehyde modification of chitosan adsorbent THB-CS
1. the preparation of chitin: after crab shell is cleaned and dried, weighing 5g, the hydrochloric acid solution leaching of 75mL 2%~6% is added
Bubble, and be stirred continuously, so that the inorganic salts in shell is dissolved and is softened, after impregnating 10~15h, removes inorganic salts.Crab shell is washed again
To neutrality, the sodium hydroxide solution of 75mL 8%~10% is added, is heated to 90 DEG C of reaction 4h.By the crab shell washing after alkali process
To neutrality, it is separately added into the KMnO of 50mL l%4And NaHSO3Solution, after rinsing respectively, clean dry obtains white solid, crust
Element.
2. the preparation of chitosan: taking dry chitin 5g, 40%~50% sodium hydroxide solution of 50mL is added, 100 DEG C anti-
Answer 7h.White chitosan solid is finally obtained, CS is abbreviated as.
3. weighing 2,3,4- tri hydroxybenzaldehyde of 0.25g and 0.5g CS in there-necked flask and 30ml methanol being added, constantly
Stirring stirs for 24 hours at 303K to dissolving, is washed out and is dried to obtain polyphenol modification of chitosan adsorbent, is labeled as THB-CS.
Described 2,3,4- tri hydroxybenzaldehydes, structural formula are as follows:
Synthetic reaction equation is as shown in Figure 1.
(2) preparation of 3,4- 4-dihydroxy benzaldehyde modification of chitosan adsorbent HBD-CS
By 2 in (one), 3,4- tri hydroxybenzaldehydes are substituted for 3,4- 4-dihydroxy benzaldehyde, the same embodiment of other steps
(1), 3,4- 4-dihydroxy benzaldehyde modification of chitosan adsorbent HBD-CS is obtained.
3, the 4- 4-dihydroxy benzaldehyde, structural formula are as follows:
(3) preparation of 4- hydroxy benzaldehyde modification of chitosan adsorbent PTD-CS
By 2 in (one), 3,4- tri hydroxybenzaldehydes are substituted for the same embodiment of his step of 4- hydroxy benzaldehyde (one), obtain 4-
Hydroxy benzaldehyde modification of chitosan adsorbent PTD-CS.
The 4- hydroxy benzaldehyde, structural formula are as follows:
(4) characterization of polyphenol modification of chitosan adsorbent
1. infrared analysis: Fig. 2 respectively illustrates the infrared spectrogram of CS, HBD-CS, PTD-CS, THB-CS.In 3440cm-1
Place is NH2Stretching vibration absworption peak.In 2950cm-1Locate corresponding to be-CH2And-CH3Asymmetric stretching vibration peak.It is modified red
In 1640cm in outer spectrogram-1Locate the absorption peak that increased peak is schiff bases C=N key, 1386cm-1Locating increased peak is phenolic hydroxyl group
The absorption peak of middle C-O key illustrates that phenolic hydroxyl structure is successfully connected to chitosan surface.
2. scanning electron microscope analysis: as shown in figure 3, chitosan is modified through phenol aldehyde modified dose, it is evident that THB-CS
Configuration of surface is in circinate, there is more empty structures.
2 polyphenol modification of chitosan of embodiment is under different acidity to the adsorption effect of germanium
Taking polyphenol modification of chitosan THB-CS, HBD-CS, PTD-CS prepared by 10mg embodiment 1 to be separately added into pH is 1
~6,20mg L-1Germanium solution in, then putting it into revolving speed is 180r/min, is shaken for 24 hours in the concussion case of temperature 303K, mistake
Filter takes filtrate and stoste to survey its concentration, calculates adsorption rate.As a result as shown in Figure 4.
From fig. 4, it can be seen that absorption property of the chitosan absorbent THB-CS of 2,3,4 tri hydroxybenzaldehydes modification to Ge (IV)
It is apparently higher than adsorbent HBD-CS, the PTD-CS modified by 3,4- 4-dihydroxy benzaldehyde and 4- hydroxy benzaldehyde, because of THB-CS
The quantity of middle phenolic hydroxyl group is relatively more, and ortho position is in structure, therefore is easier to form network and object with Ge (IV), although adjacent
The quantity of phenolic hydroxyl group is more in biphenol structure PTD-CS adsorbent, but relatively low to the adsorption rate of Ge (IV), it may be possible to because
Intramolecular hydrogen bond is formd for its own.
As seen from Figure 5, after 2,3,4 tri hydroxybenzaldehyde modification of chitosan THB-CS adsorb Ge (IV), 1300~
1700cm-1The phenolic hydroxyl group absorption peak at place is obviously reduced, and other groups do not change significantly, this explanation-OH key takes part in suction
It is attached.In addition, 3457cm-1Apparent variation also has occurred after absorption peak absorption Ge (IV) of the phenolic hydroxyl group at place, it is thus provable more
Phenol modification of chitosan THB-CS has successfully adsorbed germanium.
The equation that 2,3,4- tri hydroxybenzaldehyde modification of chitosan adsorbent THB-CS adsorbs Ge (IV) is as shown in Figure 1.
3 polyphenol modification of chitosan adsorbent of embodiment is in the presence of other rare earth ions to the separating effect of germanium
2,3,4- tri hydroxybenzaldehyde modification of chitosan adsorbent THB-CS of 10mg is weighed respectively, and 10mL concentration, which is added, is
20mg L-1Ge (IV), Mn (II), Zn (II), Ni (II), Pb (II), As (III), Co (II), Fe (III) solution, solution
PH 0~9 vibrates for 24 hours in 30 DEG C, the oscillation case of 180r/min.
As a result such as Fig. 6, in the presence of other impurities ion, THB-CS adsorbent is within the scope of pH=1-3 to Ge's (IV)
Adsorption rate is 80% or more, it can be seen that pH adsorbs As (III), Ni (II), Zn (II), Mn (II) in 0~2 range
Rate is all very low, and in 1~9 range of pH, all very low to the adsorption rate of arsenic, illustrate THB-CS adsorbent can it is a variety of from
Good selective absorption germanium ion in the presence of son.
For the practical application for verifying THB-CS.Select the acidity of analog material liquid for pH 2~3, analog material liquid group becomes Ge
(IV)(20mg L-1)、Co(II)(200mg L-1)、Ni(II)(200mg L-1).The simulation material of 10mL is added in the adsorbent of 10mg
Liquid is vibrated to adsorption equilibrium, filtering, and the content of measurement filtrate intermediate ion is simultaneously dry by the adsorbent filtered, and selects 3% after dry
NaOH is eluant, eluent.
As a result such as table 1, THB-CS is about 98% to the rate of recovery of Ge (IV), the suction to other ions Co (II), Ni (II)
Attached rate is all very low.As a result well explanation show THB-CS can in the higher situation of acidity selective recovery germanium, so
THB-CS has certain practical application.
Table one
Claims (10)
1. a kind of polyphenol modification of chitosan adsorbent, which is characterized in that preparation method includes the following steps:
1) after being cleaned and dried crab shell, hydrochloric acid solution is added and impregnates, and is stirred continuously, after impregnating 10~15h, then crab shell washed
To neutrality, sodium hydroxide solution is added, is heated to 80-100 DEG C of reaction 2-6h, is washed to neutrality, is separately added into the KMnO of l%4
And NaHSO3Solution is rinsed, dry white solid, chitin；
2) dry chitin is taken, sodium hydroxide solution is added, 80-120 DEG C of reaction 5-10h obtains white chitosan solid；
3) polyphenol and chitosan solid are placed in there-necked flask and are added methanol, be stirred continuously to dissolution, stirred at 20-50 DEG C
12-24h obtains polyphenol modification of chitosan adsorbent after washing is dry.
2. a kind of polyphenol modification of chitosan adsorbent according to claim 1, which is characterized in that in step 1), by solid-liquid
Than crab shell: hydrochloric acid=1g:10mL-20mL；The mass concentration of the hydrochloric acid is 2%~6%；By solid-to-liquid ratio, crab shell: hydrogen-oxygen
Change sodium=1g:10mL-20mL；The mass concentration of the sodium hydroxide is 8%~10%.
3. a kind of polyphenol modification of chitosan adsorbent according to claim 1, which is characterized in that in step 2), by solid-liquid
Than chitin: sodium hydroxide=1g:10mL-30mL；The mass concentration of the sodium hydroxide solution is 40%~50%.
4. a kind of polyphenol modification of chitosan adsorbent according to claim 1, which is characterized in that more described in step 3)
Phenol is one of 2,3,4- tri hydroxybenzaldehyde, 3,4- 4-dihydroxy benzaldehyde, 4- hydroxy benzaldehyde.
5. a kind of polyphenol modification of chitosan adsorbent according to claim 1, which is characterized in that in step 3), by quality
Than polyphenol: chitosan=1:1-5.
6. a kind of polyphenol modification of chitosan adsorbent according to claim 1, which is characterized in that in step 3), by solid-liquid
Than chitosan: methanol=1g:40mL-80mL.
7. application of the polyphenol modification of chitosan adsorbent described in claim 1 in recycling rare and scatter element.
8. application according to claim 7, which is characterized in that the rare and scatter element is germanium.
9. application according to claim 8, which is characterized in that in the solution of Yu Hanyou Germanium, the pH for adjusting solution is
Polyphenol modification of chitosan adsorbent described in claim 1 is added in 1-6, and at 20-50 DEG C, oscillation rate is 150~200r/min
Under, after concussion absorption 5-24h, with eluent, the eluant, eluent is the NaOH solution that concentration is 3-10%.
10. application according to claim 7, which is characterized in that press solid-to-liquid ratio, polyphenol modification of chitosan adsorbent: contain
Solution=1mg:1mL of rare earth element；The concentration containing rare and scatter element solution is 10mg L-1-100mg L-1。
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Cited By (5)
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| CN112691647A (en) * | 2020-12-08 | 2021-04-23 | 辽宁大学 | Propylene glycol modified chitosan adsorbent, preparation method thereof and application thereof in germanium adsorption |
| CN113019342A (en) * | 2021-03-09 | 2021-06-25 | 中南大学 | Preparation process of composite magnetic adsorbent, method for recovering germanium and application |
| CN113563632A (en) * | 2021-09-22 | 2021-10-29 | 南京嘉曜生物科技有限公司 | Chitosan derivative and preparation method and application thereof |
| CN113926429A (en) * | 2021-11-17 | 2022-01-14 | 辽宁大学 | Hydroxyl modified titanium dioxide composite material, preparation method thereof and application thereof in germanium recovery |
| CN114210311A (en) * | 2021-12-14 | 2022-03-22 | 中南大学 | Germanium adsorbent, preparation method and method for recovering germanium |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112691647A (en) * | 2020-12-08 | 2021-04-23 | 辽宁大学 | Propylene glycol modified chitosan adsorbent, preparation method thereof and application thereof in germanium adsorption |
| CN113019342A (en) * | 2021-03-09 | 2021-06-25 | 中南大学 | Preparation process of composite magnetic adsorbent, method for recovering germanium and application |
| CN113563632A (en) * | 2021-09-22 | 2021-10-29 | 南京嘉曜生物科技有限公司 | Chitosan derivative and preparation method and application thereof |
| CN113926429A (en) * | 2021-11-17 | 2022-01-14 | 辽宁大学 | Hydroxyl modified titanium dioxide composite material, preparation method thereof and application thereof in germanium recovery |
| CN114210311A (en) * | 2021-12-14 | 2022-03-22 | 中南大学 | Germanium adsorbent, preparation method and method for recovering germanium |
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Application publication date: 20191025 |