CN106824138A - A kind of cross-linking type polyacrylonitrile-radical amidoxim fiber and its preparation method and application - Google Patents
A kind of cross-linking type polyacrylonitrile-radical amidoxim fiber and its preparation method and application Download PDFInfo
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- CN106824138A CN106824138A CN201710170648.7A CN201710170648A CN106824138A CN 106824138 A CN106824138 A CN 106824138A CN 201710170648 A CN201710170648 A CN 201710170648A CN 106824138 A CN106824138 A CN 106824138A
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Abstract
The invention provides a kind of cross-linking type polyacrylonitrile-radical amidoxim fiber, it is prepared by following step：(1) polyacrylonitrile fibre is crosslinked with triethylene tetramine, obtains cross-linking type polyacrylonitrile fibre；(2) polyacrylonitrile fibre for obtaining upper step hydroxylamine hydrochloride amidoxim, obtains final product cross-linking type polyacrylonitrile-radical amidoxim fiber.Cross-linking type polyacrylonitrile-radical amidoxim fiber of the invention, efficiently solve the problems, such as that common amidoxim fiber cannot directly apply to bayer liquor and extract gallium, the mechanical strength of fiber is higher, higher, selective higher to the adsorption capacity of gallium simultaneously, with wide market prospects.
Description
Technical field
The present invention relates to fibrous material field, and in particular to a kind of cross-linking type polyacrylonitrile-radical amidoxim fiber and its preparation
Methods and applications.
Background technology
Gallium is a kind of important rare metal, and gallium navigates with the semi-conducting material and specific alloy of other elements composition in aviation
My god, electronics industry, new energy, the field such as communication have particularly important application.In Bauxite Ore the concentration of gallium be 20~
80ppm.During alumina producing Bayer process, about 70% gallium enters in strong basicity bayer liquor, and remaining 30% enters
In red mud.Gallium is in bayer liquor with gallic acid sodium [NaGa (OH)4] form is present, and circulate accumulation and reach 100~300mg/L.
About 90% gallium is obtained in producing the seed precipitation solution (bayer liquor) that oxygen changes aluminium from Bayer process in the world.
The method for reclaiming gallium has amalgam process, step-by-step precipitation method, solvent extraction and ion-exchange at present.Amalgam electrolysis method
Prohibitted the use of in most countries because its mercury does harm to problem.Step-by-step precipitation method long flow path, the rate of recovery are low, and introduce neutralization precipitation
Agent CO2, CaO etc., to Al2O3Production main flow have interference.Solvent extraction is expensive because of extractant, and extractant for a long time with by force
Alkaline Sodium Aluminate Solution is contacted, and solution loss is big, and the extractant of loss is not only to Al2O3Production have an impact, and to gallium in itself
Electrolysis also have an impact.Ion-exchange short flow, selectivity is good, and its feature is without adding toward in sodium aluminate solution
Any reagent, therefore it does not produce influence on main flow, by universally acknowledged to be that the best of gallium is reclaimed from sodium aluminate solution
Method.
Amidoxime group chelating resin grows up on the basis of ion exchange resin, can specially be formed with metal ion
The functional form chelating resin of chelate, it is adaptable to which coexisted in system from many kinds of metal ions carries out selection absorption to specific ion.
Turn into the first-selection of most of heavy metal ion adsorbed separation with its special structure of functional groups, property together with amino-type chelating resin
Material.Early in 1963, the aqueous solution effect of PAN fiber and azanol was prepared the chela containing amidoxime group by the Fetscher in the U.S.
Condensation material, and have studied absorbing state of these materials to elements such as uranium, copper, nickel, gold, it is indicated that this material has higher to uranium
Selectivity and adsorbance.Aamrani etc. has carried out substantial amounts of research and has found that amidoxime chelating resin is with its special functional group
Structure and absorption property and turn into the optimal material that uranium is extracted from seawater.At present, foreign scholar mainly utilizes amidoxim resin
Rare earth metal, the recovery of heavy metal ion and sewage treatment works are carried out, and achieves sizable achievement, metal ion is returned
Yield can reach more than 95%, and up to 99%, the ion concentration after treatment meets discharge standard to sewage clearance.
The domestic research to such material is also active year by year, and the ionic species that it is adsorbed also is being opened up extensively, ionic adsorption
The rate of recovery and sewage clearance are very high.Due to the high selectivity and big adsorbance of amidoxim class material, a huge sum of money is now widely used in
Belong to recovery, the treatment of waste water, basic industry, atomic energy industry, medical industry and the catalysis of the adsorbing separation, rare earth metal of ion
Deng field.
It was found that amidoxim fiber has Gao Bibiao compared to amidoxim resinae sorbing material in research before
Area, exchange velocity is fast, it is easy to be molded, the advantages of adsorbance is higher.But to it further study show that, the recycling of fiber
Poor-performing, can continuous solution loss during long-time is adsorbed to high temperature alkaline solution.
Therefore, it is necessary to search out a kind of sorbing material for being suitable for and being used under alkaline environment.
The content of the invention
To solve the above problems, the invention provides a kind of cross-linking type polyacrylonitrile-radical amidoxim fiber, it is under
State what step was prepared：
(1) polyacrylonitrile fibre is crosslinked with triethylene tetramine, obtains cross-linking type polyacrylonitrile fibre；
(2) polyacrylonitrile fibre for obtaining upper step hydroxylamine hydrochloride amidoxim, obtain final product cross-linking type polyacrylonitrile-radical together with
Amidoxime fiber.
Further, in step (1), the molecular weight of the polyacrylonitrile fibre is 30000~50000.
Further, in step (1), the triethylene tetramine is excessive.
Further, in step (1), the reaction temperature of the crosslinking is 120 DEG C~150 DEG C.
Further, in step (1), the reaction time of the crosslinking is 1~5 hour.
Further, in step (1), the reaction temperature of the crosslinking is 130 DEG C, and the reaction time is 1 hour.
Further, in step (2), the amidoxim is carried out in the environment of pH=7.
Present invention also offers the application of aforementioned polypropylene itrile group amidoxim fiber heavy metal ion in adsorbent solution.
Further, the pH value of the solution is 6~10.
Further, the heavy metal ion is gallium ion.
Further, the solution is bayer liquor.
(1. Zhao Huan is joyous, amidoxim for the amidoxim fiber bibliography based on polyacrylonitrile fibre prepared with general technology
The preparation of base polyacrylonitrile fibre and its to uranyl and competing ions Study on adsorption properties；2. once Chinese etc., containing together with amine fat Ji Ao
The preparation of condensating fiber and the research of structure and performance) compare, the advantage of the invention is that：
(1) mechanical strength of fiber is higher；
(2) alkali resistance, hydrolysis and swelling resistance are high, and good form can be kept under strongly alkaline conditions；
(3) service life cycle is long, be can be recycled in bayer liquor at least 6 times；
(4) adsorption capacity to gallium is higher, and selectivity is higher.
Obviously, the above of the invention, according to the ordinary technical knowledge and customary means of this area, is not departing from
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification of other diversified forms can also be made, is replaced or is changed.
The specific embodiment of form, remakes further specifically to the above of the invention by the following examples
It is bright.But this scope for being interpreted as above-mentioned theme of the invention should not be only limitted to following example.It is all based on the above of the present invention
The technology realized belongs to the scope of the present invention.
Brief description of the drawings
It is fine that Fig. 1 is followed successively by polyacrylonitrile fibre cloth (PANF), cross-linking type polyacrylonitrile fibre and its amidoxim from left to right
The outward appearance of Wei Bu (PAOF).
Fig. 2 is the infrared spectrogram of cross-linking type polyacrylonitrile fibre of the present invention.
Fig. 3 is the infrared spectrogram of cross-linking type polyacrylonitrile-radical amidoxim fiber of the present invention.
Fig. 4 is cross filament SEM figures under different cross linking conditions.
Fig. 5 is the adsorption capacity of the fiber to the gallium ion in bayer liquor of differential responses condition.
Fig. 6 is contrasted for a kind of adsorption capacity of 130-1-Am and commercial resin A.
Fig. 7 is the change in concentration of 130-1-Am Ga and V after level Four absorption in bayer liquor.
Fig. 8 is the level Four absorption situation contrast of 130-1-Am and two kinds of commercial resins A and B.
Fig. 9 is equilibrium adsorption curves of the 130-1-Am in bayer liquor.
Figure 10 is the desorption situation of several crosslinking amidoxim fibers.
Figure 11 is circulation absorption situation of the 130-1-Am fibers in bayer liquor.
Specific embodiment
PAN：Polyacrylonitrile fibre.Molecular weight 3 ten thousand -5 ten thousand, fiber number 2.35dtex, intensity 3.04cN/dtex.In the present invention
In specific embodiment, polyacrylonitrile fibre derives from commercially available polyacrylonitrile fibre cloth, and fiber cloth is heated in ethanol
After 80 DEG C of silicone oil on removing surface, fiber is taken standby.
Bayer liquor：Chengdu geological research institute mineral comprehensive utilizating research is provided.
PAN(CF)：Polyacrylonitrile (PAN) fiber, 3K, Jiangsu Tianniao High Technology Co., Ltd..
NH3OHHCl, AR；Tianjin Bo Di chemical inc.
NaCO3, AR：Chengdu Ke Long chemical reagents factory.
Triethylene tetramine (TETA)：Xilong Chemical Co., Ltd, CP (chemistry is pure).
The preparation of the cross-linking type polyacrylonitrile-radical amidoxim fiber of the present invention of embodiment 1
(1) by polyacrylonitrile fibre 2.12g (containing 0.04mol cyano group), 0.2mol triethylene tetramines, 0.2molH2O exists
Reacted in 100mL round-bottomed flasks, reaction temperature is 120 DEG C, and the reaction time is 1h.After completion of the reaction, cross filament is washed, 60
It is vacuum dried at DEG C, obtains cross-linking type polyacrylonitrile fibre 120-1.
(2) correspond to the ratio of 10g hydroxylamine hydrochlorides and 5.5g sodium carbonate according to 1g polyacrylonitrile fibres raw material, take cross-linking type
There is amidoximation in polyacrylonitrile fibre 120-1, adjust initial pH=7 with hydroxylamine hydrochloride/sodium carbonate, T=70 DEG C, obtain final product
Cross-linking type polyacrylonitrile-radical amidoxim fiber 120-1-Am.
The preparation of the cross-linking type polyacrylonitrile-radical amidoxim fiber of the present invention of embodiment 2
According to the method for embodiment 1, difference is that the reaction temperature of step (1) is 130 DEG C, prepares cross-linking type poly- third
Alkene nitrile fiber 130-1 and cross-linking type polyacrylonitrile-radical amidoxim fiber 130-1-Am.
The preparation of the cross-linking type polyacrylonitrile-radical amidoxim fiber of the present invention of embodiment 3
According to the method for embodiment 1, difference is that the reaction temperature of step (1) is 140 DEG C, prepares cross-linking type poly- third
Alkene nitrile fiber 140-1 and cross-linking type polyacrylonitrile-radical amidoxim fiber 140-1-Am.
The preparation of the cross-linking type polyacrylonitrile-radical amidoxim fiber of the present invention of embodiment 4
According to the method for embodiment 1, difference is that the reaction temperature of step (1) is 150 DEG C, prepares cross-linking type poly- third
Alkene nitrile fiber 150-1 and cross-linking type polyacrylonitrile-radical amidoxim fiber 150-1-Am.
The preparation of the cross-linking type polyacrylonitrile-radical amidoxim fiber of the present invention of embodiment 5
According to the method for embodiment 1, difference is that the reaction temperature of step (1) is 150 DEG C, and the reaction time is 5h.Prepare
Obtain cross-linking type polyacrylonitrile fibre 150-5 and cross-linking type polyacrylonitrile-radical amidoxim fiber 150-5-Am.
The structural characterization of the cross-linked fiber of the present invention of embodiment 6
Polyacrylonitrile fibre cloth (PANF), cross-linking type polyacrylonitrile fibre of the present invention and and its amidoxim fiber cloth (PAOF)
Outward appearance it is as shown in Figure 1.
(1) IR Characterization result
Fig. 2 and Fig. 3 are respectively the infared spectrums of the cross-linking type polyacrylonitrile fibre obtained under different cross linking conditions, wherein respectively
Group fiber is respectively to be crosslinked at 120/140/150 DEG C at 1h (embodiment 1,3,4) and 150 DEG C and is crosslinked 5h (embodiment 5)
Sample.
As can be seen that as temperature raises the extension with the reaction time, the amination crosslinking degree of fiber increases,
2234cm-1- CN the vibration peaks at place weaken up to being wholly absent, and illustrate that nitrile group content reduction, amine groups content increase.
(2) elementary analysis result
The elementary analysis result of cross-linking type polyacrylonitrile fibre of the present invention, PAN and PAN (CF) is as shown in table 1.
The elementary analysis of each group cross filament of table 1
(3) ESEM characterization result
The ESEM (SEM) of cross-linking type polyacrylonitrile fibre 120-1,140-1,150-1 and 150-5 is as shown in Figure 4.
(4) elementary analysis of the amidoxim fiber prepared under different crosslinking temperatures
The elementary analysis result of amidoxim fiber is as shown in table 2 under different crosslinking temperatures.
Amidoxim fiber elementary analysis prepared under the different crosslinking temperatures of table 2 (crosslinking time is 1h)
* atomic percentage
The gallium ion adsorption test of the cross-linked fiber of the present invention of embodiment 7
1st, absorption of the amidoxim fiber to gallium ion under different cross linking conditions
Bayer liquor (Bayer liquid) is to produce Al from Bayer process2O3During seed precipitation solution, herein made
Bayer liquor composition such as table 3.
The bayer liquor composition of table 3
(1) Static Adsorption test：Each 50mL of several pieces bayer liquor is taken, is separately added into 100mL ground conical flasks, added
A certain amount of amidoxim fiber, vibrates absorption at 45 DEG C.The simulated solution before and after absorption is taken respectively, using ICP-AES inductance couplings
Close plasma emission spectrum and determine Ga therein3+Content, adsorbance is calculated according to formula 1-1.
Wherein CtAnd C0Respectively t and starting ionic concentration, m is the quality of adsorbent, and V is the volume of adsorbate.
By 4 groups of cross filaments --- after 120-1-Am, 140-1-Am, 150-1-Am, 150-5-Am amidoxim, to visiing
The adsorption capacity of the gallium ion in ear solution is as shown in Figure 5.As can be seen that with the increase of amination crosslinking degree, amidoxim is fine
The performance of the absorption gallium ion of dimension also constantly strengthens.
It is the superiority of protrusion fiber of the present invention, is compared using a kind of pearl polyacrylie-type crosslinking commercial resins,
As shown in fig. 6, the absorption property (9.16mg/g) of fibrous material is significantly higher than commercial resin (acrylic type, 1.98mg/g).
(2) Dynamic Adsorption test is intended：PAOF adds 1g, bayer liquor 50mL every time, every time absorption about 2h.Taken out after absorption
Saturation fiber, then put into new fiber, absorption situation when bayer liquor crosses post during simulating actually used.For across comparison
To the absorption property of gallium ion in bayer liquor, we contrast and with reference to two kinds of commercial resins A and B (trade mark of Resin A is PAOF
Ch-920, resin B is D-526).Plan Dynamic Adsorption test has been carried out to it (resin adds 2g, weight in wet base every time).Inhaled by level Four
The change in concentration of Ga and V is as shown in Figure 7 in attached bayer liquor：
In the bayer liquor that we test, by after 4 grades of absorption of PAOF, the gallium in solution is substantially completely removed, and
The decline of vanadium is not then obvious.This explanation PAOF has good Selective adsorption to gallium ion, can not only be in the aluminium of high concentration
Effective enrichment gallium ion in environment, moreover it is possible to suppress the absorption of competition vanadium.
Contrast in such as Fig. 8,4 grades of absorption properties of PAOF illustrate of the invention on two kinds of commercial polymeric adsorbents
Fiber adsorbing material has the advantages that rapidly and efficiently.
(3) adsorption equilibrium curve：By in 0.5g fibers input 60ml bayer liquors, taken out every certain time interval
1ml solution, ion concentration therein, the equilibrium adsorption time with clear and definite fiber in bayer liquor are determined in ICP-AES methods.
Fig. 9 is PAOF to gallium in bayer liquor and the equilibrium adsorption curve of vanadium, it can be seen that amidoxim fiber is molten to Bayer
, 140min or so (simulation bayer liquor is 60min), (simulation is molten for saturated adsorption capacity 17.6mg/g for the saturated adsorption time of liquid
Liquid is 26.9mg/g).PAOF is relatively low to the adsorbance of V, so fluctuation is relatively large, does not embody obvious equilibrium tendency.
Absorption-the desorption performance of 2.PAOF
Various absorption of the crosslinking amidoxim fiber to gallium ion and the desorption data using acid of hydrochloric acid and nitric acid are as shown in Figure 10.
From the point of view of desorption data, the hydrochloric acid and nitric acid of 1mol/L can well be desorbed the gallium ion on fiber, and resolution factor reaches 85%
More than.
The cyclic test of the cross-linked fiber of the present invention of embodiment 8
Experiment proves, do not carry out precrosslink amidoxim fiber just occur after first use in bayer liquor it is serious molten
It is swollen and be partly dissolved, it is impossible to recycle.And by the amidoxim fiber of triethylene tetramine precrosslink, can be in bayer liquor
Middle recycling 6 times also keeps good form.Result is as shown in figure 11.
In sum, the present invention efficiently solves common amidoxim fiber and cannot directly apply to bayer liquor extraction gallium
Problem, while the mechanical strength of fiber is higher, higher, selective higher to the adsorption capacity of gallium, with wide market prospects.
Claims (11)
1. a kind of cross-linking type polyacrylonitrile-radical amidoxim fiber, it is characterised in that：It is prepared by following step：
(1) polyacrylonitrile fibre is crosslinked with triethylene tetramine, obtains cross-linking type polyacrylonitrile fibre；
(2) polyacrylonitrile fibre for obtaining upper step hydroxylamine hydrochloride amidoxim, obtains final product cross-linking type polyacrylonitrile-radical amidoxim
Fiber.
2. polyacrylonitrile-radical amidoxim fiber according to claim 1, it is characterised in that：In step (1), the polypropylene
The molecular weight of nitrile fiber is 30000~50000.
3. polyacrylonitrile-radical amidoxim fiber according to claim 1, it is characterised in that：In step (1), the triethylene
Tetramine is excessive.
4. the polyacrylonitrile-radical amidoxim fiber according to claim any one of 1-3, it is characterised in that：In step (1), institute
The reaction temperature for stating crosslinking is 120 DEG C~150 DEG C.
5. polyacrylonitrile-radical amidoxim fiber according to claim 4, it is characterised in that：In step (1), the crosslinking
Reaction time is 1~5 hour.
6. polyacrylonitrile-radical amidoxim fiber according to claim 5, it is characterised in that：In step (1), the crosslinking
Reaction temperature is 130 DEG C, and the reaction time is 1 hour.
7. the polyacrylonitrile-radical amidoxim fiber according to claim any one of 1-6, it is characterised in that：In step (2), institute
State amidoxim is carried out in the environment of pH=7.
8. the application of polyacrylonitrile-radical amidoxim fiber heavy metal ion in adsorbent solution described in any one of claim 1-7.
9. application according to claim 8, it is characterised in that：The pH value of the solution is 6~10.
10. the application according to claim 9 or 10, it is characterised in that：The heavy metal ion is gallium ion.
11. apply according to claim 10, it is characterised in that：The solution is bayer liquor.
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| CN109231344A (en) * | 2018-10-30 | 2019-01-18 | 中国工程物理研究院核物理与化学研究所 | A kind of polyamines class uranium absorption material and preparation method thereof |
| CN109289803A (en) * | 2018-09-29 | 2019-02-01 | 西南科技大学 | Polyamines base/amidoxime group modification polyfunctional group ion-exchange fibre method of preparation and use |
| CN109482159A (en) * | 2018-12-03 | 2019-03-19 | 中广核达胜加速器技术有限公司 | A kind of amidoxim composite fibre and preparation method thereof |
| CN109776744A (en) * | 2019-01-12 | 2019-05-21 | 广西大学 | A kind of amidoxim-silica resin preparation method for adsorbing gallium |
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