CN106732432B - A kind of chitosan/persimmon tannin composite material and preparation method and the application in Ti recovery - Google Patents

A kind of chitosan/persimmon tannin composite material and preparation method and the application in Ti recovery Download PDF

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CN106732432B
CN106732432B CN201710034982.XA CN201710034982A CN106732432B CN 106732432 B CN106732432 B CN 106732432B CN 201710034982 A CN201710034982 A CN 201710034982A CN 106732432 B CN106732432 B CN 106732432B
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chitosan
composite material
persimmon tannin
germanium
persimmon
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CN106732432A (en
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熊英
龚利凤
单炜军
娄振宁
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Liaoning University
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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
    • 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
    • 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
    • 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
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention relates to a kind of chitosan/persimmon tannin composite material and preparation method and the applications in Ti recovery.The technical solution adopted is that: it takes chitosan in three-necked flask, suitable ethanol solution is added, then instill epoxychloropropane solution, then react at a certain temperature, it is cooling, it filters, washing obtains intermediate product to neutrality.Persimmon tannin is placed in another reaction vessel, deionized water is added, adjusting pH is 9-10, and intermediate product is added, it is cooling after mixture is stirred 6 hours at 40-50 DEG C, it filters, washing obtains chitosan/persimmon tannin composite material CS-Cl-PT to neutrality.Chitosan produced by the present invention/persimmon tannin composite material, can from the mixed solution containing germanium and arsenic selective absorption germanium, not only economize on resources, environment-protecting clean, and being with a wide range of applications.

Description

A kind of chitosan/persimmon tannin composite material and preparation method and in Ti recovery Application
Technical field
The invention belongs to the preparation of composite material and to the extractive technique field of dissipated metal, and in particular to a kind of shell is poly- Sugar/persimmon tannin composite material and preparation method and the application in Ti recovery.
Background technique
Germanium is a kind of rare and scatter element, and abundant in China's germanium resource, storage capacity ranks first in the world, and has been widely used for space flight The fields such as aviation, light communication, infrared optics, electronic device, solar battery, biomedicine.Have now found that germanium mineral have 11 Kind, it is primarily present in Namibia's germanium silicon, germanite, calcium germanium alum, itoite, germanium iron-stone and germanium magnetic iron ore, but germanium is on ground Without independent deposit in shell, more associations are in Non-ferrous minerals, and content is low, and distribution is wide, currently, mainly from zinc metallurgy and combustion Germanium is extracted in the by-product of coal.
Currently, having chlorization distillation method, resin adsorption method, microemulsion method, zinc dust precipitation there are many kinds of the methods of Ti recovery Method, ion-exchange, extraction and electrolysis method, in addition there are also the acid-hatching of young eggs, alkaline leaching, combination method, in alkali fusion-it is legal and Vacuum melting method etc..Once a large amount of exploration had been done in China in terms of solvent extraction, it is the weight of separation, enrichment germanium compound Method is wanted, the extractant of common extracted germanium is broadly divided into three classes.First is that respectively with LIX 63 for the hydroxyl oximes of representative and with Kelex 100 is the quinolines of representative, this kind of extractants is external product mostly；Second is that amine extractant, there is N235 in the country, but There are no examples of industrial application；Third is that hydroximic acid, such as H106 (the different hydroxamic acid of tridecyl tertiary carbon), YW100,7815, HGS98 Deng this kind of extractants is generally domestic-developed, but there are still some problems in industrial application for these extractants.And utilize biology Composite material Ti recovery from the waste liquid of germanium, not only economizes on resources, but also environment-protecting clean, can be widely applied to agricultural and work In industry waste material, there is very big prospect in industrial application.
At the same time, persimmon tannin is a kind of natural biological copolymer, in China's persimmon abundance, is occupied first of the world, Its structure be comprising several o-dihydroxies and adjacent triatomic aromatic rings (poly- hydroxyl polyphenol), can be used as a kind of multidentate ligand with Complex reaction occurs for metal ion, so the metal ion in energy efficient absorption and selective binding solution, however persimmon list It rather is highly soluble in water, be easy to cause solable matter therein to dissolve and adsorption capacity is caused to reduce, oxygen demand increase etc. in water Problem.
Summary of the invention
Present invention is generally directed to persimmon tannins to be highly soluble in water, and solable matter therein is be easy to cause to dissolve and cause to inhale The problems such as attached ability reduces, oxygen demand increases in water proposes " chitosan and both biological materials of persimmon tannin carry out It is compound " viewpoint, select and only utilized using low-level or existing obsolete Pericarpium Kaki and chitosan is raw materials, study it to waste liquid The recycling ability of middle germanium, the method for the present invention is easy to operate, environment-protecting clean, and resource utilization is high, high to the selectivity of germanium, processing week Phase is short, and can be recycled, and has very high practical value.
The present invention is achieved through the following technical solutions: a kind of chitosan/persimmon tannin composite material (CS-Cl-PT), Preparation method includes the following steps:
1) chitosan (CS) is mixed with ethanol solution, then instills epoxychloropropane, react 3-4h at 70 DEG C -85 DEG C, It is cooling, it filters, washs to neutrality, obtain intermediate product CS-Cl；
2) persimmon tannin is dissolved in deionized water, adjusting pH is 9-10, and intermediate product CS-Cl is added, and is uniformly mixed, will It is cooling after mixture stirs 6-7h at 40-50 DEG C, it filters, washs to neutrality, obtain target product chitosan/persimmon list Peaceful composite material CS-Cl-PT.
A kind of above-mentioned chitosan/persimmon tannin composite material, the volume fraction of the ethanol solution are 40%- 55%.
A kind of above-mentioned chitosan/persimmon tannin composite material, in mass ratio, chitosan: epoxychloropropane=2:2-7.
A kind of above-mentioned chitosan/persimmon tannin composite material, in mass ratio, chitosan: persimmon tannin=1.5-2.5: 4。
A kind of above-mentioned chitosan/persimmon tannin composite material, the adjusting pH is 9-10, using NaOH, Na2CO3Or NaHCO3Any aqueous slkali.
The synthetic route of CS-Cl-PT of the present invention is as follows:
Chitosan prepared by the present invention/application of the persimmon tannin composite material in Ti recovery.Method is as follows: adjusting germanic Above-mentioned chitosan/persimmon tannin composite material, concussion absorption 24-48h is added in the pH=8-10 of solion.Use eluant, eluent It is eluted, the eluant, eluent is the NaOH solution of 50% ethanol solution of 1-3mol/L HCl, 0.75-2.0mol/L.
The beneficial effects of the present invention are:
1, abundance: China is that persimmon cultivated area is maximum in the world at present, the highest country of persimmon fruit yield, and this hair Bright persimmon tannin is just taken from Pericarpium Kaki.
2, easy to operate: the present invention is compound by chitosan and persimmon tannin by simple chemical treatment method, synthesizes Journey is simple and safe.
3, low in cost: biological material used in the present invention is the waste that people usually abandon, and is almost not necessarily to cost, Also relatively easy to its processing method, cost is greatly lowered.
4, in the present invention, under certain acidity, composite material has biggish adsorbance to the germanium in waste liquid, and uses 50% ethanol solution of 1mol/L HCl and the NaOH solution of 1.5-2.0mol/L can elute the germanium of absorption.
5, the composite material of the persimmon tannin obtained by the present invention and chitosan can be from the mixing of the arsenic and germanium of high concentration The Ti recovery in practical feed liquid may be implemented in selective absorption germanium in solution.
6, of the invention, biological adsorption material of the chitosan as natural green, the metal active with amino and methylol Site, chelation can occurs with various metals ion in itself, can also be compound with other a variety of biological materials progress, this Chitosan is successfully combined with each other by invention with persimmon tannin, not only realizes the reasonable utilization to biological material, but also Good selectivity is adsorbed with to germanium in solution, is with a wide range of applications and application field.
7, the composite material of chitosan and persimmon tannin prepared by the present invention can from the waste liquid of germanium Ti recovery, this is compound Biological material used in the preparation of material is energy saving, cheap, abundance, has stronger actual application ability.
Detailed description of the invention
Fig. 1 is the infrared figure after chitosan/persimmon tannin composite material prepared by embodiment 1 and its absorption germanium.
Fig. 2 is the scanning electron microscope (SEM) photograph after chitosan/persimmon tannin composite material prepared by embodiment 1 and its absorption germanium.
Fig. 3 be embodiment 2 prepare chitosan/persimmon tannin composite material at different pH to the adsorption rate of Ge (IV).
Fig. 4 is that chitosan/persimmon tannin composite material prepared by embodiment 1 separates germanium from the arsenic solution containing high concentration Effect statistical chart.
Specific embodiment
A kind of chitosan of embodiment 1/persimmon tannin composite material
(1) preparation method
1) it takes 2g chitosan (CS) in three-necked flask, 50% (v/v) ethanol solution of 40mL is added, then instill the ring of 4g Oxygen chloropropane solution reacts 3h at 80 DEG C, cooling, filters, is first washed with ethyl alcohol, then neutrality is washed with deionized water, Obtain intermediate product CS-Cl.
2) persimmon tannin of 4g is placed in another reaction vessel, the deionized water of 80mL is added, adjusting pH with NaOH is 10, intermediate product CS-Cl is added, after then heating at 45 DEG C by mixture and stir 6h, filtering is first carried out with dilute HCl Washing, then neutrality is washed till with deionization.Product after drying for 24 hours, is ground up, sieved, finally obtaining partial size is in 50 DEG C of baking oven 100-150 μm of chitosan/persimmon tannin composite material CS-Cl-PT.
(2) result
1) Fig. 1 is respectively the infrared spectrogram of CS, CS-Cl, CS-Cl-PT, CS-Cl-PT load Ge (IV).3451cm-1Place Absorption peak be-NH2With-OH characteristic absorption peak, 3000-2700cm-1Absorption peak be C-H stretching vibration peak.Compare CS and The infrared spectrum of CS-Cl is found: 1640-1600cm in CS-1There is stronger-NH2In-plane bending peak, but this peak in CS-Cl It dies down and narrows, illustrate-the NH of CS2It is reacted with epoxychloropropane；730cm in CS-Cl-1There is the infrared absorption of C-Cl at place Peak, it was demonstrated that CS successfully reacts with epoxychloropropane.Compare the infrared spectrum discovery of CS-Cl and CS-Cl-PT: CS-Cl-PT In the infrared absorption peak of-OH obviously weaken, illustrate that a part of hydroxyl of tannin takes part in reaction, while in 2347cm-1Place is free Hydrogen bond peak disappear, further prove that tannin and chitosan are successfully compound.Compare CS-Cl-PT and CS-Cl-PT load Ge (IV) Infrared spectrum discovery: 1400cm in CS-Cl-PT-1There is the in-plane bending vibration peak of-OH at place, and CS-Cl-PT loads Ge (IV) The in-plane bending vibration peak of-OH disappears in infrared spectrum, but in 2347cm-1There is the absorption peak of free hydrogen bond, it was demonstrated that CS-Cl- - OH functional group takes part in the absorption of Ge (IV) in PT, while there are also the generations of hydrogen bond.
2) in Fig. 2, (a) and (b) be respectively persimmon tannin and persimmon tannin and Chitosan Composites scanning electron microscope (SEM) photograph, Wherein there are many strip fragments in the scanning electron microscope (SEM) photograph of tannin, and in irregular distribution；And persimmon tannin and chitosan are multiple The scanning electron microscope (SEM) photograph surface relative smooth of condensation material, and there is more fold and duct, destroy the structure of tannin.
A kind of chitosan of embodiment 2/persimmon tannin composite material is under different acidity to the adsorption effect of germanium
(1) preparation method
1) it takes the chitosan of 1.5g, 2g, 2.5g respectively in 3 three-necked flasks, it is molten that 40mL, 50% (v/v) ethyl alcohol is added Liquid, then the epoxychloropropane of 4g is instilled, 3h is reacted at 80 DEG C, it is cooling, it filters, is first washed with ethyl alcohol, then use deionized water Neutrality is washed, intermediate product CS-Cl is obtained.
2) persimmon tannin of 4g is respectively placed in 3 different reaction vessels, each deionized water that 80mL is added is used NaOH adjust pH be 10, be separately added into intermediate product CS-Cl obtained above, mixture is heated at 45 DEG C and stir 6h it Afterwards, it filters, is first washed with dilute HCl, then be washed with deionized water to neutrality.3 kinds of different products are dry in 50 DEG C of baking oven After for 24 hours, be ground up, sieved, finally obtain chitosan that partial size is 3 kinds of 100-150 μm different chitosans and persimmon tannin ratio/ Persimmon tannin composite material.
(2) result
Take above-mentioned chitosan/persimmon tannin composite material of 10mg be added separately to pH be 1,3,6,8,10 10mL, In the germanium solution of 20ppm, then puts it into concussion case and shaken under the revolving speed of 180r/min, at a temperature of 303K for 24 hours, mistake Filter, takes filtrate and stoste to survey its adsorption rate.As a result as shown in Figure 3.
As seen from Figure 3, chitosan/persimmon tannin composite material is maximum to the rate of recovery of germanium when pH is 8-10, and three kinds are not Material in proportion is all up to 80% or more the adsorption rate of germanium.
A kind of chitosan of embodiment 3/persimmon tannin composite material is from the arsenic solution containing high concentration to germanium separating effect
The mixed liquor of the 1ppmAs and 1ppmGe of existing pH=10,10ppmAs and 1ppmGe mixed liquor, The mixed liquor of 50ppmAs and 1ppmGe, the mixed liquor of 80ppmAs and 1ppmGe, 100ppmAs and 1ppmGe mixture Liquid takes the above-mentioned feed liquid of 10mL respectively, and chitosan/persimmon tannin composite material prepared by 10mg embodiment 1 is added, and shakes 24 hours Later, it filters, measures the concentration of stoste and filtrate.As a result as shown in Figure 4.
From fig. 4, it can be seen that the content with As (III) in solution increases, the adsorbance of Ge (IV) is barely affected, because This, it can be deduced that conclusion, in solution the concentration ratio of the concentration of As (III) and Ge (IV) be within 100:1 all will not to chitosan/ Persimmon tannin composite material impacts the selectivity of Ge (IV), and composite material synthesized by the present invention can be from containing high concentration As (III) waste water in selective recovery Ge (IV).
Elution effect of the acid-base solution of 4 various concentration of embodiment to the composite material of load germanium
1) in the germanium solution for the 200ppm that the CS-Cl-PT for weighing the preparation of embodiment 1 of 100mg is added to 100mL, concussion It takes out and filters after 48h, the composite material of adsorption saturation is dried
2) composite material after drying is mixed with the eluent of various concentration with solid-to-liquid ratio 1:1, after concussion for 24 hours It takes out and filters, survey the concentration of germanium ion in solution, the results are shown in Table 1.
3) as shown in Table 1,1mol/L HCl in50% ethyl alcohol, 1.5mol/L NaOH-2.0mol/LNaOH are to load germanium Composite material elution effect it is best, be all up to 97% or more.
Elution effect of the different eluents of table 1 to germanium
A kind of chitosan of embodiment 5/cycle performance of the persimmon tannin composite material on Ti recovery
Method is as follows: taking the germanium solution of the 200ppm of 100mL, the shell that the preparation of embodiment 1 of 100mg is added thereto is poly- Sugar/persimmon tannin composite material shakes 48h, adsorbs to the germanium metal in solution, be computed the composite material pair of 1000mg The load capacity of germanium metal is 36mg or so, and the composite material for loading germanium is washed with deionized water to neutrality after filtering, adds The ethyl alcohol of 1mol/L HCl-50% or the HCl of 1.5-2.0mol/L are parsed, its elution amount is calculated, by five suctions After attached-parsing circulation, as shown in Table 2, the rate of recovery still can reach 85% or more, it is seen that the chitosan and persimmon tannin it is compound Material has good recycling ability to the recycling of germanium.
The absorb-elute circular list of 2 CS-Cl-PT of table

Claims (3)

1. a kind of utilize chitosan/persimmon tannin composite material Ti recovery method, it is characterised in that method is as follows: adjusting germanic PH=8-10 of solion is added chitosan/persimmon tannin composite material and is washed after 24-48h is adsorbed in concussion with eluant, eluent De-, the eluant, eluent is the NaOH solution or 2.0mol/L of 50% ethanol solution of 1mol/L HCl, 1.5mol/L NaOH solution；The chitosan/persimmon tannin composite material preparation method includes the following steps:
It 1) is that 40%-55 % ethanol solution mixes, then instills epoxychloropropane with volume fraction by chitosan, at 70 DEG C -85 DEG C 3-4h is reacted, it is cooling, it filters, washs to neutrality, obtain intermediate product CS-Cl；
2) persimmon tannin is dissolved in deionized water, adjusting pH is 9-10, and intermediate product CS-Cl is added, and is uniformly mixed, will mix It is cooling after conjunction object stirs 6-7h at 40-50 DEG C, it filters, washs to neutrality, obtain target product chitosan/persimmon tannin Composite material CS-Cl-PT.
2. the method as described in claim 1, it is characterised in that: in mass ratio, chitosan: epoxychloropropane=2: 2-7.
3. the method as described in claim 1, it is characterised in that: in mass ratio, chitosan: persimmon tannin=1.5-2.5: 4.
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CN109046252B (en) * 2018-07-20 2021-06-18 辽宁大学 Carbon nanotube and gallnut tannin composite material, preparation method thereof and application thereof in gallium recovery
CN111229175B (en) * 2020-01-17 2023-06-23 中国林业科学研究院资源昆虫研究所 Immobilized tannin for enriching rare earth metals, preparation method and method for enriching rare earth metals by using immobilized tannin
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
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101992064A (en) * 2009-08-25 2011-03-30 付华峰 Method for preparing novel tannic acid curing chitosan heavy metal ion adsorbent
CN101992077A (en) * 2009-08-25 2011-03-30 付华峰 Preparation method of tannic acid curing chitosan microsphere heavy metal ion adsorbent
CN105289519A (en) * 2015-10-19 2016-02-03 辽宁大学 Persimmon tannin adsorbent and preparing method and application thereof

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* Cited by examiner, † Cited by third party
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US8642088B2 (en) * 2009-09-04 2014-02-04 Wisconsin Alumni Research Foundation Tannin-chitosan composites

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101992064A (en) * 2009-08-25 2011-03-30 付华峰 Method for preparing novel tannic acid curing chitosan heavy metal ion adsorbent
CN101992077A (en) * 2009-08-25 2011-03-30 付华峰 Preparation method of tannic acid curing chitosan microsphere heavy metal ion adsorbent
CN105289519A (en) * 2015-10-19 2016-02-03 辽宁大学 Persimmon tannin adsorbent and preparing method and application thereof

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