CN106582552A - Glutamic acid modified chitosan adsorbent as well as preparation method and application thereof - Google Patents
Glutamic acid modified chitosan adsorbent as well as preparation method and application thereof Download PDFInfo
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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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention relates to a glutamic acid modified chitosan adsorbent as well as a preparation method and application thereof. The preparation method comprises the following steps: dissolving chitosan into an acetic acid solution, adding tetraethoxysilane (TEOS), carrying out stirring for 30 to 40 min, adding aqueous ammonia, carrying out stirring for 24 to 26 hours, carrying out suction filtering, washing with ethyl alcohol till the mixture is neutral, and carrying out vacuum drying to obtain CS-SiO2; mixing CS-SiO2 with the ethyl alcohol aqueous solution, adding epoxy chloropropane, carrying out refluxing at the temperature of 70 DEG C for 3 hours to obtain a product, cooling and filtering the product, washing the product with water and the ethyl alcohol, and drying the washed product to obtain an intermediate product I; and dissolving glutamic acid into a sodium carbonate solution, adding the intermediate product I, carrying out refluxing at the temperature of 80 DEG C for 24 hours to obtain a product, cooling and filtering the product, washing with distilled water till the product is neutral, and carrying out drying to obtain SiO2-CS-Glu. The adsorbent prepared based on the preparation method goes green, is environment-friendly, pollution-free and high in separation and enrichment efficiency, can avoid waste of rare earth resources, and is also applicable to selectively adsorbing scandium from a solution mixed with rare earth ions.
Description
Technical field
The invention belongs to the preparation of green adsorbent and rare earth metal extractive technique field, and in particular to a kind of glutamic acid changes
Property chitosan absorbent preparation and its from low concentration of rare earth solution be enriched with rare earth ion method.
Background technology
Rare earth element (REs) refers to III B races in the periodic table of elements, atomic number be 21 scandium (Sc), 39 yttrium (Y), with
And the lanthanide series of the lutecium (Lu) of 57 lanthanum (La) -71, totally ten seven elements.With scientific research and the development of technology, rare earth element
Range of application in each functional material constantly expands, and the high-new scientific researches such as new forms of energy, biological and information new material have progressively been become
With the main support material of technical field.Since the nineties in 20th century, rare-earth trade is even more and has obtained swift and violent development.With dilute
Soil resource develops the reinforcement of dynamics and being continuously increased for rare earth supply and demand, and high-grade Rare Earth Mine is gradually decreased, and due to national strategy
The purpose of protection of resources, the exploitation to rare earth resources is put forward higher requirement, and this certainly will need to strengthen low-grade complex rare earth
The exploitation of ore deposit.Although rare earth element is generally treated not as a kind of toxic metals, is had with regard to rare earth element to thin
Bacterium, the report of plant and animal toxicity, and as a large amount of rare earths are constantly discharged in environment, can predict following several
Environmental problem is necessarily brought in 10 years, the stricter environmental protection policy for heavy metals is also necessarily had and is put into effect.Additionally, having
That what is discharged in a little industrial processes is regarded as a kind of important secondary resource and is recycled containing RE waste water.Therefore,
No matter from protection of resources or the angle of environmental conservation, it is required for strengthening returning low concentration of rare earth feed liquid or waste water middle rare earth
Receive the research of isolation technics.
Consumption and consumption figure of China's rare earth in terms of new technique, new material industry was improved rapidly since in recent years, was
The pure rare earth of high-quality is obtained, extract and separate is one of conventional method.At present, the conventional extractant of China's rare-earth trade
Main to include neutral TBP, P305, Cyanex923 and acidic extractant P507, these extractants are in rare-earth industry application
Also all come with some shortcomings part while widely：TBP is to the distribution coefficient of metal ion than relatively low, it usually needs
Strong acid and salting-out agents could realize extraction under conditions of existing；Although P305 has higher extraction yield and larger separation factor,
But P305 contains the substantial amounts of reducing impurity for being difficult and eliminating, and its synthesis is relatively costly, limits to a certain extent
Its application；Cyanex923 synthesis is difficult, and price is higher, hinders the paces of its commercial Application；Acidic extractant P507 weights
Rare earth element back extraction acidity is high, and is difficult to back extraction completely, and the time that extraction reaches balance is longer, more ammonia nitrogen is produced after saponification and is given up
Water causes environmental pollution.
Many biomass can adsorb and enriched in metals ion from solution, be superior adsorbent.Biomass adsorbent is more
Natural biopolymer or derivatives thereof or even biomass castoff are adopted for raw material, with wide material sources, species is various,
It is with low cost, the characteristics of renewable and bio-compatible；Biomass adsorbent is not only nontoxic, it is easy to biodegradation, and past
Toward containing abundant carboxyl, amino, hydroxyl isoreactivity functional group, easy complexation of metal ions is also easy to further repairing for adsorbent
Decorations, are a kind of green adsorbing materials with applications well prospect.Biomass adsorbent is widely used in purification of waste water and metal
Ion enrichment is separated.
The content of the invention
For the problem that prior art is present, it is an object of the invention to bio-waste is rationally utilized, it is useless from life
Gurry-Carapax Eriocheir sinensiss are raw material, through extracting shitosan and then being simply modified for from norium solion
Separation and concentration scandium.The operational approach of the present invention is simple, and low cost is pollution-free, energy free consumption, energy-conserving and environment-protective.
The technical solution used in the present invention is that a kind of glutamic acid modification of chitosan adsorbent, preparation method is as follows：
1) dissolve chitosan in acetic acid solution, add tetraethyl orthosilicate (TEOS), stir 30-40min, add ammonia
Aqueous solution, stirs 24-26h, and sucking filtration is washed till neutrality with ethanol, is vacuum dried, and obtains CS-SiO2；
2) by CS-SiO2After mixing with ethanol water, epoxychloropropane is added, flow back 3h at 70 DEG C, cooling is filtered,
With water and washing with alcohol, it is dried, obtains intermediate product I；
3) glutamic acid is dissolved in sodium carbonate liquor, adds intermediate product I, flow back 24h at 80 DEG C, cooling, sucking filtration, with steaming
Distilled water is washed till neutrality, is dried, and obtains glutamic acid modification of chitosan adsorbent (SiO2-CS-Glu)。
A kind of above-mentioned glutamic acid modification of chitosan adsorbent, described shitosan comes from Carapax Eriocheir sinensis.
A kind of above-mentioned glutamic acid modification of chitosan adsorbent, described acetic acid solution, concentration expressed in percentage by volume is 1-3%；
Described ammonia spirit, concentration expressed in percentage by volume is 2-4%.
Above-mentioned a kind of glutamic acid modification of chitosan adsorbent, by solid-liquid ratio, CS-SiO2:Epoxychloropropane=1g:5mL-
20mL。
A kind of above-mentioned glutamic acid modification of chitosan adsorbent, the concentration of described sodium carbonate liquor is 1.0-2.0mol/
L。
A kind of above-mentioned glutamic acid modification of chitosan adsorbent, in mass ratio, intermediate product I:Glutamic acid=1:4-10.
Application of the above-mentioned glutamic acid modification of chitosan adsorbent in absorption rare earth ion.Preferably, described rare earth
Ion is scandium.Method is as follows：The solution containing rare earth ion is taken, pH to 5.25-5.62 is adjusted, adds above-mentioned glutamic acid to be modified
Chitosan absorbent, concussion absorption.Preferably, with the HCl of 0.2-0.4mol/L as eluant.
The present invention, adsorbent SiO2The synthetic route of-CS-Glu is as follows：
The invention has the beneficial effects as follows：
1. glutamic acid modification of chitosan adsorbent separation and concentration efficiency high of the invention, preparing, can from mischmetal from
Selective absorption scandium in the solution of son.
2. the consumption of method of the present invention energy free, energy-conserving and environment-protective, adsorbance it is big, widely applicable, with practical application.
3. abundant raw material of the present invention：The shitosan raw material sources of the present invention are in discarded biological substance Carapax Eriocheir sinensiss.
4. the present invention is pollution-free：Used in the inventive method solvent can Reusability, therefore dirt will not be caused to environment
Dye.
5. low cost of the present invention：Processing cost is greatly lowered, and processing cost is the 10-20% of traditional treatment method.
6. the present invention is applied widely：The present invention is adapted to the solution of any one rare earth ion, for mischmetal
Metal ion solution can be with selective absorption scandium.
7. of the invention, under certain acidity, the glutamic acid modification of chitosan adsorbent of preparation rare earth ion is had compared with
Big adsorbance, and can be by the metal recovery of absorption using 0.3mol/L HCl solutions.
Description of the drawings
Fig. 1 is SiO prepared by embodiment 12The adsorption isotherm of-CS-Glu adsorbents absorption Sc (III).
Fig. 2 is SiO prepared by embodiment 12The infrared spectrogram of-CS-Glu adsorbents.
Fig. 3 is SiO prepared by embodiment 12- CS-Glu is under different acidity to the absorption behavior of rare earth ion.
Fig. 4 is resolution factor of the mineral acid of variable concentrations to load Sc- adsorbents.
Fig. 5 is from low concentration of rare earth leachate adsorption and enrichment rare-earth process flow chart.
Specific embodiment
Embodiment 1
(1) preparation method
1) shitosan：Appropriate Carapax Eriocheir sinensiss are taken, Carapax Eriocheir sinensis powder is ground to obtain, 5% HCl solution immersion 12h is added, is removed solvable
Property impurity.Filter, after being dried, add 40% NaOH solution, at 100 DEG C 7h is reacted, obtain final product white solid shitosan CS.
2) 2g CS are dissolved in the acetic acid solution that 100mL concentration expressed in percentage by volumes are 2%, add 30mL TEOS stirrings
30min or so；In adding mixture to the ammonia that 200mL concentration expressed in percentage by volumes are 3%, 24h is stirred, sucking filtration is washed with ethanol
To neutral, 24h is vacuum dried, obtains matrix material CS-SiO2；
3) 1g CS-SiO are taken2It is added to ethanol water (v:V=1:1) in, it is subsequently adding 10mL epoxychloropropane, 70
Flow back 3h at DEG C, cooling, filters, and with water and washing with alcohol, is dried, and obtains intermediate product I；
4) 2.5g glutamic acid 50mL are taken, the sodium carbonate liquor of 1.5mol/L dissolves, addition 0.5g intermediate product I, 80 DEG C
Lower backflow 24h, cooling, sucking filtration is washed to neutrality with distillation, is dried, that is, obtain glutamic acid modification of chitosan adsorbent SiO2-
CS-Glu。
(2) result
1) as shown in figure 1, the adsorbent is 31.7mg/g to the saturated extent of adsorption of scandium ion.Absorption meets Langmuir suctions
Attached isotherm model, illustrates adsorbent SiO2Absorption of-the CS-Glu to rare earth ion belongs to monolayer adsorption.
2) Fig. 2 is respectively CS, SiO2- CS-Glu, SiO2Infrared spectrogram after-CS-Glu absorption Sc (III) ions.
3451cm-1The absworption peak at place is-NH in CS2With-OH characteristic absorption peaks, 2904cm-1For the stretching vibration peak of c h bond, 1096cm-1The absworption peak at place is the stretching vibration peak of Si-O-Si, in 1734cm after glutamic acid modification shitosan-1There is new peak in place, the peak
It is the characteristic absorption peak of C=O on carboxyl, illustrates that glutamic acid has successfully been connected on shitosan.
Embodiment 2
(1) preparation method
1) shitosan：With embodiment 1.
2) 2g CS are dissolved in the acetic acid solution that 100mL concentration expressed in percentage by volumes are 2%, add 30mL TEOS stirrings
30min or so；In adding mixture to the ammonia that 200mL concentration expressed in percentage by volumes are 3%, 24h is stirred, sucking filtration is washed with ethanol
To neutral, 24h is vacuum dried, obtains matrix material CS-SiO2；
3) 1g CS-SiO are taken2It is added to ethanol water (v:V=1:1) in, it is subsequently adding 15mL epoxychloropropane, 70
Flow back 3h at DEG C, cooling, filters, and with water and washing with alcohol, is dried, and obtains intermediate product I；
4) 2.5g glutamic acid 50mL are taken, the sodium carbonate liquor of 1.5mol/L dissolves, addition 0.5g intermediate product I, 80 DEG C
Lower backflow 24h, cooling, sucking filtration is washed to neutrality with distillation, is dried, that is, obtain glutamic acid modification of chitosan adsorbent SiO2-
CS-Glu。
(2) result
The adsorbent is to the solution of the 20ppm scandiums of pH=4 with solid-to-liquid ratio as 1:1 carries out concussion absorption, shakes under 298K
24h, to the adsorption efficiency of scandium 72.6% can be reached.
Embodiment 3
(1) preparation method
1) shitosan：With embodiment 1.
2) 2g CS are dissolved in the acetic acid solution that 100mL concentration expressed in percentage by volumes are 2%, add 30mL TEOS stirrings
30min or so；In adding mixture to the ammonia that 200mL concentration expressed in percentage by volumes are 3%, 24h is stirred, sucking filtration is washed with ethanol
To neutral, 24h is vacuum dried, obtains matrix material CS-SiO2；
3) 1g CS-SiO are taken2It is added to ethanol water (v:V=1:1) in, it is subsequently adding 10mL epoxychloropropane, 70
Flow back 3h at DEG C, cooling, filters, and with water and washing with alcohol, is dried, and obtains intermediate product I；
4) 5g glutamic acid 50mL are taken, the sodium carbonate liquor dissolving of 1.5mol/L adds 0.5g intermediate product I, at 80 DEG C
Backflow 24h, cooling, sucking filtration is washed to neutrality with distillation, is dried, that is, obtain glutamic acid modification of chitosan adsorbent SiO2-CS-
Glu。
(2) result
The adsorbent is to the solution of the 20ppm scandiums of pH=4 with solid-to-liquid ratio as 1:1 carries out concussion absorption, shakes under 298K
24h, to the adsorption efficiency of scandium 73.7% can be reached.
The SiO of embodiment 42- CS-Glu is under different acidity to the separating effect of scandium in norium solion.
PH 2.16, pH 3.48, pH 4, pH 4.95, pH 5.25, pH 5.46, pH 5.62 are taken respectively, and concentration is respectively
The Sc of 20ppm, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, the mixed solution 10mL of Y-ion, respectively
The SiO for adding 10mg embodiments 1 to prepare2- CS-Glu adsorbents, concussion absorption 24h, determine each ion concentration, such as Fig. 3 in solution
It is shown.
It can be seen from figure 3 that as pH value must increase, SiO2- CS-Glu gradually increases the adsorption rate of scandium, in pH=5.25-
When 5.62, SiO2Absorption of-the CS-Glu to scandium can reach more than 90%, and to the La in addition to scandium, Ce, Pr, Nd, Sm,
Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y-ion do not adsorb substantially, and adsorption rate is respectively less than 20%.Generally using selectivity because
Sub- Sela/bTo judge the size of adsorbent separating power, Sela/bThe bigger separating power for representing adsorbent of value is bigger, SelSc/M>
When 1, you can efficiently separate.Sc (III) ions are as shown in table 1 with the selectivity factor of other metal ions at pH 5.62, from
As can be seen that all data are all higher than 1.99 in table, separation can be fully achieved.
The SiO of table 12- CS-Glu adsorbs the selectivity factor of rare earth ion
Eluting effect of the mineral acid of the variable concentrations of embodiment 5 to load Sc- adsorbents.
1) the adsorbent SiO of the preparation of 200mg embodiments 1 is accurately weighed2- CS-Glu, is added to 200mL, 50ppm (pH4)
Scandium standard solution in, after balance to be adsorbed, filter, drying is saturated with the adsorbent of sum.
2) be saturated with sum by dry adsorbent and variable concentrations (0.05mol/L, 0.1mol/L, 0.3mol/L,
0.5mol/L, 1mol/L, 2mol/L) mineral acid with solid-to-liquid ratio as 1:1 ratio is shaken, and is surveyed in filtrate after concussion 24h
The concentration of scandium ion, as shown in Figure 4.
As seen from Figure 4：The eluting effect of hydrochloric acid is better than sulphuric acid, and as the increase eluting of concentration of hydrochloric acid takes the lead in increasing
Reduce after big, the eluting rate of the HCl of 0.3mol/L is maximum, can eluting completely, eluting rate can reach more than 90%.
The SiO of embodiment 62- CS-Glu adsorbs the method for rare earth ion from the rare earth infusion solution of low concentration
Method is as follows：Adsorbent SiO prepared by embodiment 12- CS-Glu is added in the re dip solution of low concentration,
Rare earth ion is adsorbed, after balance to be adsorbed, desorbing is carried out to adsorbent with the HCl of 0.3mol/L, obtain rare-earth enrichment
Liquid.The process chart of adsorption and enrichment rare earth ion is as shown in Figure 5.Table 2 is 10mg adsorbent SiO2- CS-Glu is to Sc's (III)
Load capacity, four adsorption-desorption cycles have been carried out to it.10mg adsorbent SiO in four circulation experiments2- CS-Glu is to Sc
(III) load capacity is respectively 0.307mg, 0.295mg, 0.299mg, 0.298mg, and every time circulation back loading amount does not almost become
Change, the adsorbent at least can be recycled four times, and the response rate is respectively 91.75%, 90.85%, 92.30%, 91.76%.
Adsorbent SiO in sum2- CS-Glu successfully can adsorb rare earth ion from the rare earth infusion solution of low concentration, and
And adsorbent can be recycled.
The SiO of table 22The absorb-elute circular list of-CS-Glu
Claims (10)
1. a kind of glutamic acid modification of chitosan adsorbent, it is characterised in that preparation method is as follows：
1) dissolve chitosan in acetic acid solution, add tetraethyl orthosilicate, stir 30-40min, add ammonia spirit, stir
24-26h is mixed, sucking filtration is washed till neutrality with ethanol, be vacuum dried, obtain CS-SiO2；
2) by CS-SiO2After mixing with ethanol water, add epoxychloropropane, flow back 3h at 70 DEG C, cooling is filtered, with water and
Washing with alcohol, is dried, and obtains intermediate product I；
3) glutamic acid is dissolved in sodium carbonate liquor, adds intermediate product I, flow back 24h at 80 DEG C, cooling, sucking filtration uses distilled water
Neutrality is washed till, is dried, obtain glutamic acid modification of chitosan adsorbent.
2. a kind of glutamic acid modification of chitosan adsorbent as claimed in claim 1, it is characterised in that：Described shitosan from
In Carapax Eriocheir sinensis.
3. a kind of glutamic acid modification of chitosan adsorbent as claimed in claim 1, it is characterised in that：Described acetic acid solution,
Concentration expressed in percentage by volume is 1-3%；Described ammonia spirit, concentration expressed in percentage by volume is 2-4%.
4. a kind of glutamic acid modification of chitosan adsorbent as claimed in claim 1, it is characterised in that：By solid-liquid ratio, CS-SiO2:
Epoxychloropropane=1g:5mL-20mL.
5. a kind of glutamic acid modification of chitosan adsorbent as claimed in claim 1, it is characterised in that：Described sodium carbonate liquor
Concentration be 1.0-2.0mol/L.
6. a kind of glutamic acid modification of chitosan adsorbent as claimed in claim 1, it is characterised in that：In mass ratio, it is middle to produce
Thing I:Glutamic acid=1:4-10.
7. application of the arbitrary described glutamic acid modification of chitosan adsorbent of claim 1-6 in absorption rare earth ion.
8. application as claimed in claim 7, it is characterised in that described rare earth ion is scandium.
9. application as claimed in claim 7, it is characterised in that method is as follows：Take the solution containing rare earth ion, adjust pH to
5.25-5.62, adds the arbitrary described glutamic acid modification of chitosan adsorbent of claim 1-6, concussion absorption.
10. application as claimed in claim 9, it is characterised in that with the HCl of 0.2-0.4mol/L as eluant.
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| CN114671483A (en) * | 2022-03-24 | 2022-06-28 | 重庆文理学院 | Method for recovering nickel in electroplating wastewater by using modified chitosan |
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