CN109012586A - Uranium absorption agent and preparation method thereof - Google Patents
Uranium absorption agent and preparation method thereof Download PDFInfo
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- CN109012586A CN109012586A CN201810929763.2A CN201810929763A CN109012586A CN 109012586 A CN109012586 A CN 109012586A CN 201810929763 A CN201810929763 A CN 201810929763A CN 109012586 A CN109012586 A CN 109012586A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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Abstract
The invention discloses a kind of uranium absorption agent comprising carbon nanotube and low-temperature plasma graft are in the amidoxime group in carbon nano tube surface.The uranium absorption agent has large specific surface area, the advantage that selectivity is high, adsorption capacity is big, speed is fast, environmental-friendly, has good adsorption capacity to uranium.The invention also discloses the preparation method of above-mentioned uranium absorption agent, comprising steps of S1, using Low Temperature Plasma Treating carbon nanotube, obtain amide carbon nano tube；S2, hydroxylamine hydrochloride alcohol solution is prepared, and its pH is adjusted to neutrality；S3, amide carbon nano tube is added into neutral hydroxylamine hydrochloride alcohol solution, at least 8h is reacted at 60 DEG C~80 DEG C, products therefrom is washed to neutral and dry, obtains uranium absorption agent.The preparation method, which only passes through non-thermal plasma trap, to graft on amidoxime group on the surface of carbon nanotube, simple process, low in cost, environmentally friendly without raw materials such as concentrated acids, and the combination of the two is also stronger.
Description
Technical field
The invention belongs to adsorbent preparation technical fields, it relates in particular to a kind of uranium absorption agent and preparation method thereof.
Background technique
Uranium is as a kind of important natural radioactive element, and either in terms of the nuclear power for benefiting the mankind or relationship is national
The core science and technology aspect of safety all has a decisive role.Uranium used at present be mostly leached from uranium ore, but with
Increasingly increase of the countries in the world to uranium demand, the equilibrium of supply and demand of uranium are gradually broken, and people are urgently in the unconventional uranium of searching to guarantee
Its long term growth, then the imagination of the extraction of uranium from seawater is come into being.But URANIUM IN SEAWATER content is low, and treating capacity is big, to meet certain
Production requirement expends huge.Compared with seawater, the uranium content in salt lake bittern wants much higher.China Caidamu Basin salt lake saturation
In brine and the mountain Qaidam Basin Nan Ji oil field water, the content of uranium is than high 1000 times of uranium content or so in seawater.Small
The salt lake Si Kule is located at the Qinghai Province Caidamu Basin northwestward, and average uranium content is 320 μ g/L, respectively bavin in the salt lake bittern
Up to tub salt lake bittern, world's seawater, the 3.3 of the horizontal mean value in world river, 97,627 times, not only considerably beyond URANIUM IN SEAWATER
Concentration, and also above the average value in Caidamu Basin salt lake.It is processed in addition, researcher also found by salt pan solarization
In saturation magnesium chloride raw brine after (extracting boron, lithium etc.), the content of uranium can be enriched to 4mg/L.This saturated bittern passes through
After simple processing, the content of uranium can reach 60mg/L, be 20,000 times of URANIUM IN SEAWATER content.It can thus be seen that in salt lake
It is more at low cost than the extraction of uranium from seawater and be easier to realize that the uranium of high concentration can undoubtedly make salt lake bittern mention uranium, more Development volue.
Currently, the processing method in relation to uranium in solution mainly has the precipitation method, ion-exchange, floatation and absorption method etc.,
This case that salt lake bittern complicated component, other methods are compared, use is easy to operate, and the high absorption method of separation and Extraction rate is more
It is suitble to extract uranium from salt lake bittern.In general, mainly there is following requirement to adsorbent: (1) adsorption capacity is big；(2)
Adsorption rate is fast；(3) high to the adsorptive selectivity of uranium；(4) adsorbent is easily recycled, can be quickly desorbed；(5) good mechanical property, it is right
Chemistry and microorganism are stablized.Currently, for mention the adsorbent of uranium according to its chemical structure be roughly divided into inorganic and organic this
Two major classes adsorbent.Inorganic adsorbent, the usually compound of alkaline earth metal element or transition metal element, as leaded is closed
The compounds such as object, manganese dioxide, hydrous titanium oxide (HTO), basic zinc carbonate.Although in laboratory research find manganese dioxide,
Hydrous titanium oxide, zeolite, ferriferous oxide, sepiolite etc. have strong suction-operated to uranium, but general all to the absorption choosing of uranium
Selecting property is poor, the influence vulnerable to high ionic strength.Organic adsorbent is primarily referred to as the macromolecule with certain selection adsorption function
Polymer or biomass.
Although current portion of techniques discloses the preparation method of the uranium absorption agent of different compositions, absorption property is also carried out
Certain description, but be directed to the description of specific practical brine systems adsorbing separation uranium and report less.Actual salt lake bittern, oil
The complicated composition of water in field, underground heat aqueous systems, trace uranium therein coexist with a variety of other Ordinary ions, the Ordinary ion pair coexisted
The adsorbing separation interference of uranium is very big.In addition, the intensity of adsorbent and separation are also the important of selected adsorbent in addition to absorption property
Index.
To sum up, current uranium absorption agent is low in the presence of selectivity, adsorption capacity is small, stability is poor, easily pollutes the environment
Equal shortcomings.
Summary of the invention
To solve the above-mentioned problems of the prior art, the present invention provides a kind of uranium absorption agent and preparation method thereof, should
Uranium absorption agent has that large specific surface area, selectivity is high, adsorption capacity is big, speed is fast, environmental-friendly, good cycling stability excellent
Gesture has good adsorption capacity to uranium.
In order to achieve the above object of the invention, present invention employs the following technical solutions:
A kind of uranium absorption agent comprising carbon nanotube and low-temperature plasma graft are in the carbon nano tube surface
Amidoxime group.
Further, the grafting amount of the amidoxime group is 80%~85%.
Further, the carbon nanotube is magnetic modified carbon nano-tube.
Further, the equilibrium adsorption capacity of the uranium absorption agent is 3.8mg/g~4.1mg/g.
Another object of the present invention is to provide a kind of preparation methods of uranium absorption agent, comprising steps of
S1, using Low Temperature Plasma Treating carbon nanotube, obtain amide carbon nano tube；
S2, hydroxylamine hydrochloride alcohol solution is prepared, and its pH is adjusted to neutrality；
S3, the amide carbon nano tube is added into neutral hydroxylamine hydrochloride alcohol solution, it is anti-at 60 DEG C~80 DEG C
At least 8h is answered, products therefrom is washed to neutral and dry, obtains uranium absorption agent.
Further, in the step S1, the carbon nanotube is magnetic modified carbon nano-tube；The magnetism carbon modified
Nanotube the preparation method comprises the following steps:
S11, ferric chloride solution is prepared；
S12, unmodified carbon nanotube is added into the ferric chloride solution, and is uniformly dispersed, obtain suspension；
S13, under protective atmosphere, frerrous chloride and ammonium hydroxide are added into the suspension, flows back at 60 DEG C~100 DEG C
At least 1h, it is dry after cooling washing, obtain the magnetic modified carbon nano-tube.
Further, in the step S12, iron chloride and the unmodified carbon nanotube in the ferric chloride solution
Mass ratio is 1.2~2.4:1~2.
Further, in the step S13, the frerrous chloride and the unmodified carbon nanotube in the suspension
Mass ratio is 1~2.5:1~2.
Further, the step S1 method particularly includes:
The carbon nanotube and grafted monomers are mixed, gained mixture is placed in reaction of low temperature plasma device；Its
In, the grafted monomers are dimethyl amide or diaminomaleonitrile；The carbon nanotube and the dimethyl amide
Ratio is 1g/400mL~1g/500mL, and the ratio of the carbon nanotube and the diaminomaleonitrile is 1g/50mL~1g/
100mL；
Under protective atmosphere, the mixture reacts at 200 DEG C~400 DEG C of temperature and the discharge power of 10W~20W
At least 30min obtains the amide carbon nano tube.
Further, in the step S3, the hydroxylamine hydrochloride and amide in the hydroxylamine hydrochloride alcohol solution of the neutrality
The mass ratio of carbon nano tube is 1.1g~2g:0.5g~1g.
The present invention grafts on amidoxime group on the surface of carbon nanotube by using lower temperature plasma technology, thus
Form a kind of completely new uranium absorption agent；The uranium absorption agent because have large specific surface area, selectivity is high, adsorption capacity is big, speed is fast,
Environmental-friendly, good cycling stability advantage, and good adsorption capacity is embodied with good adsorption capacity to uranium.This hair
The preparation method of the above-mentioned uranium absorption agent of bright offer, carbon can be grafted on for amidoxime group by only passing through non-thermal plasma trap
On the surface of nanotube, the modification means of covalent bond or non-covalent bond are used compared to the prior art, it is simple process, at low cost
It is honest and clean, it is environmentally friendly without raw materials such as concentrated acids, and the combination of the two is also stronger without generation covalent bond or non-covalent
The exception that finishing coat is easy to fall off when key is modified.
Detailed description of the invention
What is carried out in conjunction with the accompanying drawings is described below, above and other aspect, features and advantages of the embodiment of the present invention
It will become clearer, in attached drawing:
Fig. 1 is the cyclical stability test chart of uranium absorption agent in the embodiment of the present invention 4；
Fig. 2 is pair of the time of equilibrium adsorption and equilibrium adsorption capacity of different uranium absorption agent in comparative experiments 1 of the invention
Than figure；
Fig. 3 is the comparison diagram of the selective absorption of different uranium absorption agent in comparative experiments 2 of the invention.
Specific embodiment
Hereinafter, with reference to the accompanying drawings to detailed description of the present invention embodiment.However, it is possible to come in many different forms real
The present invention is applied, and the present invention should not be construed as limited to the specific embodiment illustrated here.On the contrary, providing these implementations
Example is in order to explain the principle of the present invention and its practical application, to make others skilled in the art it will be appreciated that the present invention
Various embodiments and be suitable for the various modifications of specific intended application.
The present invention provides a kind of uranium absorption agent comprising carbon nanotube and low-temperature plasma graft are received in the carbon
Amidoxime group on nanotube surface.
Preferably, the grafting amount of amidoxime group is 80%~85%.
In this way, the amidoxime group grafted in carbon nano tube surface can be used as uranium identification point, high selection is realized to uranium
It property and specifically adsorbs, and the carbon nanotube as carrier then can be grafted more amidoxime groups because of its bigger serface
Group；In this way, the equilibrium adsorption capacity of the uranium absorption agent can reach 3.8mg/g~4.1mg/g.
Further, carbon nanotube is magnetic modified carbon nano-tube, in this way, can be from when using the uranium absorption agent
In water body to be adsorbed quickly, efficiently separate, reduction be generally separated operation caused by molten damage problem.
The preparation method of above-mentioned uranium absorption agent will be described in detail below.
The preparation method of uranium absorption agent of the invention includes the following steps:
In step sl, using Low Temperature Plasma Treating carbon nanotube, amide carbon nano tube is obtained.
Specifically, amide carbon nano tube the preparation method comprises the following steps: firstly, carbon nanotube and grafted monomers are mixed, will
Gained mixture is placed in reaction of low temperature plasma device；Then, under protective atmosphere, by aforementioned mixture in 200 DEG C~400
DEG C temperature and 10W~20W discharge power under react at least 30min, i.e., acquisition amide carbon nano tube.
More specifically, grafted monomers can be dimethyl amide or diaminomaleonitrile；When grafted monomers are diformazan
When base diamides, then the ratio for controlling carbon nanotube and dimethyl amide is 1g/400mL~1g/500mL, and when grafting is single
When body is diaminomaleonitrile, then the ratio for controlling carbon nanotube and diaminomaleonitrile is 1g/50mL~1g/100mL.
Above-mentioned carbon nanotube is preferably magnetic modified carbon nano-tube, in this way, then answering before preparing amide carbon nano tube
Magnetization modification is carried out in advance to common unmodified carbon nanotube in the ban.
Specifically, the method for modifying of the magnetism modified carbon nano-tube are as follows: S11, prepare ferric chloride solution；S12, to chlorination
Unmodified carbon nanotube is added in ferrous solution, and is uniformly dispersed, obtains suspension；S13, under protective atmosphere, into suspension
Frerrous chloride and ammonium hydroxide is added, few 1h is back at 60 DEG C~100 DEG C, it is dry after cooling washing, that is, obtain magnetic carbon modified
Nanotube.Then the magnetism modified carbon nano-tube can be mixed with above-mentioned grafted monomers and is placed in reaction of low temperature plasma device
Middle progress amidation processing.
Further, during above-mentioned magnetization modification, iron chloride and unmodified carbon nanometer in ferric chloride solution are controlled
The mass ratio of pipe is 1.2~2.4:1~2；And the mass ratio of the unmodified carbon nanotube in frerrous chloride and suspension is 1
~2.5:1~2.
Such as, firstly, weighing 4g~8g FeCl3·6H2O is added in 200mL deionized water, and it is molten that dissolution obtains iron chloride
Liquid；It is dispersed in the ferric chloride solution secondly, weighing the unmodified carbon nanotube of 2g~4g again, ultrasonic 30min or so, and machinery stirs
12h is mixed, suspension is obtained；Third step, in N2Under atmosphere, 2g~5g FeCl is added into the suspension2·4H2It is molten to heat this by O
Liquid is rapidly added 8mL~15mL ammonium hydroxide (NH to 90 DEG C4OH, 30%), continue the 1h that flows back at 90 DEG C, be cooled to room temperature, spend
Ion is washed to neutrality repeatedly；Finally, being placed in a vacuum drying oven washed product in 70 DEG C or so freeze-day with constant temperature, magnetic is obtained
Property modified carbon nano-tube.
In step s 2, hydroxylamine hydrochloride alcohol solution is prepared, and its pH is adjusted to neutrality.
Specifically, 1.1g~2g hydroxylamine hydrochloride can be added in 100mL conical flask, the mixing for adding first alcohol and water is molten
Liquid 80mL~120mL (volume ratio is preferably 2:3), it is to be dissolved completely after, a certain amount of sodium hydroxide is added by pH and is adjusted to 7.0
Left and right.
In step s3, amide carbon nano tube is added into neutral hydroxylamine hydrochloride alcohol solution, in 60 DEG C~80 DEG C
Lower reaction at least 8h, products therefrom is washed to neutral and dry, obtains uranium absorption agent.
Specifically, the quality of the hydroxylamine hydrochloride and amide carbon nano tube in neutral hydroxylamine hydrochloride alcohol solution is controlled
Than for 1.1g~2g:0.5g~1g.
At the same time, when after reaction, being preferably washed with deionized after filtration product and be solid to neutrality, and in 60 DEG C
Freeze-day with constant temperature controls for 24 hours in the vacuum oven controlled.
Above-mentioned uranium absorption agent and preparation method thereof and beneficial effect, but ability will be embodied by specific embodiment below
Field technique personnel will be understood by, and the present invention is not limited to listed by following several embodiments, following embodiments are only that above-mentioned uranium is inhaled
Attached dose and preparation method thereof of specific example.
Embodiment 1
Firstly, weighing 4.52g FeCl3·6H2O is added in 200mL deionized water, obtains ferric chloride solution.
Then, it weighs the unmodified nanotube of 2g to be dispersed in the ferric chloride solution, ultrasonic 30min, then mechanical stirring 12h,
Obtain stable suspension.
Third step, in N2Under atmosphere, 1.83g FeCl is added to suspension2·4H2O heats the solution to 70 DEG C, rapidly
8mL ammonium hydroxide (NH is added4OH, 30%), continue the 1h that flows back at 70 DEG C, be cooled to room temperature, be washed to neutrality repeatedly with deionization,
Vacuum oven is placed into 70 DEG C of freeze-day with constant temperature, obtains magnetic carbon nano-tube.
Magnetic carbon nano-tube and dimethyl amide are mixed according to the ratio of 0.5g/200mL, are placed in low temperature by the 4th step
Plasma reactor PDC-32G-2, Harrick Plasma) in, it is passed through N2, temperature be 250 DEG C, discharge power 10W
Under conditions of handle 30min, obtain amide carbon nano tube.
1.1g hydroxylamine hydrochloride is added in 100mL conical flask, adds the mixed solution 80mL of first alcohol and water for 5th step
(volume ratio 2:3), it is to be dissolved completely after, a certain amount of sodium hydroxide is added by the pH of solution and is adjusted to 7.0.
Finally, 0.5g amide carbon nano tube is added into the neutral hydroxylamine hydrochloride alcohol solution of above-mentioned acquisition, in 60
DEG C~80 DEG C at react 8h, reaction product is filtered after reaction and uses deionized water repeated flushing to weakly acidic pH, at 60 DEG C
Freeze-day with constant temperature is for 24 hours to get the magnetic carbon nano-tube for arriving amidoxim in vacuum oven, using as uranium absorption agent.
In this way, in the present embodiment, that is, providing a kind of uranium absorption agent comprising magnetic modified carbon nano-tube and low temperature
Plasma grafting is in the amidoxime group in the magnetism modified carbon nano tube pipe surface, and the grafting amount of amidoxime group is
82.97%.
Embodiment 2
Firstly, weighing 6.61g FeCl3·6H2O is added in 200mL deionized water, obtains ferric chloride solution.
Then, it weighs the unmodified nanotube of 3g to be dispersed in the ferric chloride solution, ultrasonic 30min, then mechanical stirring 12h,
Obtain stable suspension.
Third step, in N2Under atmosphere, 2.72g FeCl is added to suspension2·4H2O heats the solution to 90 DEG C, rapidly
10mL ammonium hydroxide (NH is added4OH, 30%), continue the 1h that flows back at 90 DEG C, be cooled to room temperature, be washed to repeatedly with deionization
Property, vacuum oven is placed into 70 DEG C of freeze-day with constant temperature, obtains magnetic carbon nano-tube.
Magnetic carbon nano-tube and dimethyl amide are mixed according to the ratio of 0.8g/300mL, are placed in low temperature by the 4th step
Plasma reactor PDC-32G-2, Harrick Plasma) in, it is passed through N2, temperature be 320 DEG C, discharge power 15W
Under conditions of handle 1h, obtain amide carbon nano tube.
1.5g hydroxylamine hydrochloride is added in 100mL conical flask, adds the mixed solution 100mL of first alcohol and water for 5th step
(volume ratio 2:3), it is to be dissolved completely after, a certain amount of sodium hydroxide is added by the pH of solution and is adjusted to 7.0.
Finally, 0.8g amide carbon nano tube is added into the neutral hydroxylamine hydrochloride alcohol solution of above-mentioned acquisition, in 60
DEG C~80 DEG C at react 8h, reaction product is filtered after reaction and uses deionized water repeated flushing to weakly acidic pH, at 60 DEG C
Freeze-day with constant temperature is for 24 hours to get the magnetic carbon nano-tube for arriving amidoxim in vacuum oven, using as uranium absorption agent.
In this way, in the present embodiment, that is, providing a kind of uranium absorption agent comprising magnetic modified carbon nano-tube and low temperature
Plasma grafting is in the amidoxime group in the magnetism modified carbon nano tube pipe surface, and the grafting amount of amidoxime group is
84.26%.
Embodiment 3
Firstly, weighing 9.05g FeCl3·6H2O is added in 200mL deionized water, obtains ferric chloride solution.
Then, it weighs the unmodified nanotube of 4g to be dispersed in the ferric chloride solution, ultrasonic 30min, then mechanical stirring 12h,
Obtain stable suspension.
Third step, in N2Under atmosphere, 3.69g FeCl is added to suspension2·4H2O heats the solution to 90 DEG C, rapidly
15mL ammonium hydroxide (NH is added4OH, 30%), continue the 1h that flows back at 90 DEG C, be cooled to room temperature, be washed to repeatedly with deionization
Property, vacuum oven is placed into 70 DEG C of freeze-day with constant temperature, obtains magnetic carbon nano-tube.
Magnetic carbon nano-tube and dimethyl amide are mixed according to the ratio of 1g/500mL, are placed in low temperature etc. by the 4th step
Plasma reactor PDC-32G-2, Harrick Plasma) in, it is passed through N2, temperature is 380 DEG C, discharge power is 20W's
Under the conditions of handle 2h, obtain amide carbon nano tube.
2g hydroxylamine hydrochloride is added in 100mL conical flask, adds the mixed solution 120mL (body of first alcohol and water for 5th step
Product than be 2:3), it is to be dissolved completely after, a certain amount of sodium hydroxide is added by the pH of solution and is adjusted to 7.0.
Finally, 1g amide carbon nano tube is added into the neutral hydroxylamine hydrochloride alcohol solution of above-mentioned acquisition, in 60 DEG C
8h is reacted at~80 DEG C, after reaction filters reaction product and uses deionized water repeated flushing to weakly acidic pH, it is true at 60 DEG C
Freeze-day with constant temperature is for 24 hours to get the magnetic carbon nano-tube for arriving amidoxim in empty drying box, using as uranium absorption agent.
In this way, in the present embodiment, that is, providing a kind of uranium absorption agent comprising magnetic modified carbon nano-tube and low temperature
Plasma grafting is in the amidoxime group in the magnetism modified carbon nano tube pipe surface, and the grafting amount of amidoxime group is
83.14%.
In order to verify the adsorption effect for the uranium absorption agent that the various embodiments described above obtain, following experiments have been carried out.
The uranium absorption agent that 0.03g above-described embodiment 1, embodiment 2 and embodiment 3 are prepared is accurately weighed respectively, it is static
The salt lake the Qinghai Province 50mL small Si Kule intercrystalline bittern is adsorbed (through uranium in inductively coupled plasma body transmitting mass spectrograph measurement brine
Initial concentration is 3.41mg/L), adsorption temp is room temperature, does not need to adjust solution ph.It is as shown in table 1 to adsorb situation.
Adsorption effect of the uranium absorption agent to uranium in brine in 1 Examples 1 to 3 of table
It can be seen from Table 1 that uranium absorption agent provided by the above embodiment shows good adsorption capacity to uranium, put down
Weighing apparatus adsorbance can be up to 3.8mg/g~4.1mg/g.
Uranium absorption agent of the invention can generally be regenerated by acid solution, to be recycled, as using 1mol/L
Hydrochloric acid solution is regenerated.
In order to illustrate the good cyclical stability of uranium absorption agent of the invention, following embodiments have been carried out.
Embodiment 4
In example 4, the uranium absorption agent that an equilibrium adsorption capacity is 0.25mg/g is had chosen, its adsorption uranium is made to reach flat
After weighing apparatus, supported sorbents are obtained；Then regeneration treatment is carried out to supported sorbents using the hydrochloric acid solution of 1mol/L, and using again
Reproducing adsorbent after life carries out adsorption/desorption circulation experiment, investigates it and recycles performance.
In the present embodiment, experiment condition is controlled specifically: the initial concentration of uranium is 0.25mgL in brine-1, brine
PH is 4.00 ± 0.05, and adsorption temp is (25 ± 1) DEG C；Also, the additive amount for controlling the uranium absorption agent in the present embodiment is
0.67g/L carries out absorption test using the uranium absorption agent of 0.67g the present embodiment in i.e. every liter of brine.
The cycle performance of uranium absorption agent used by the present embodiment is as shown in Figure 1.From figure 1 it appears that by five
After adsorption/desorption cyclic process, uranium the uranium absorption agent surface of the present embodiment adsorbance by initial 0.25mg/g it is slight under
0.197mg/g is dropped to, shows that salt acid soak can make to load the supported sorbents effective regeneration after uranium, adsorption capacity is lost very
Small, slightly decreasing for adsorbance is primarily due to caused by not exclusively desorption herein.
It is indicated above that the hydrochloric acid of 1mol/L can effectively make the supported sorbents regeneration after adsorption uranium, and adsorbing
It is reused in the case where the substantially no loss of amount.Simultaneously consider the uranium absorption agent Magneto separate characteristic, can easily from
It is recycled in brine, therefore can guarantee that it is recycled during long-term brine treatment with lower replacement cost.
In addition, the selectivity of uranium absorption agent of the invention is high, adsorption capacity is big, fireballing feature in order to embody, carry out
Following comparative experimentss.
In following comparative experimentss, adsorbent is common carbon nanotube as a comparison, i.e., is grafted without amidoxime group
Carbon nanotube.
In following comparative experimentss 1, by Staticadsorption experiment compared common carbon nanotube and the present invention in together with amine
The carbon nanotube of oximido group's grafting is to the absorption property of uranium in brine, such as time of equilibrium adsorption and equilibrium adsorption capacity.
Comparative experiments 1
In order to probe into influence of the time to adsorption process, the concentration of uranium in brine is measured by sampling in different duration of oscillation,
As a result it is shown in Fig. 2.In this comparative experiments, experiment condition is controlled specifically: the initial concentration of uranium is 0.55mgL in brine-1,
The pH of brine is 4.00 ± 0.05, and adsorption temp is (25 ± 1) DEG C；Also, the uranium absorption agent and comparison in the control present invention are inhaled
Attached dose of additive amount is 0.67g/L, i.e. carries out absorption test using 0.67g adsorbent in every liter of brine.
As shown in Figure 2, in the initial phase of absorption, adsorption capacity is increased rapidly with the increase of duration of oscillation, centainly
After time, adsorption capacity tends towards stability, and absorption reaches balance.Wherein, in the uranium absorption agent (AO-CNTs) of uranium in the present invention
Absorption only needs 0.5h to can reach adsorption equilibrium, and the absorption on common carbon nanotube (UN-CNTs) then needs 8h that could reach
Equilibrium adsorption capacities to adsorption equilibrium, and uranium absorption agent of the invention also greatly increase.
In order to effectively carry out separation and concentration to uranium, the selectivity of adsorbent is particularly important.Due to the ion in brine at
Point complex, some coexisting ions may be adsorbed simultaneously, and then influence the absorption of uranium, therefore of the invention in order to assess
The adsorptive selectivity of uranium absorption agent
Comparative experiments 2
This comparative experiments probed into uranium absorption agent of the invention and common carbon nanotube respectively to other in brine coexist from
Son (B2O3、Ca2+、K+、Li+、Mg2+、Na+、SO4 2-) absorption situation, corresponding selectivity factor is shown in Fig. 3.In this comparison
In experiment, experiment condition is controlled specifically: the initial concentration of uranium is 0.25mgL in brine-1, adsorption temp is (25 ± 1) DEG C；
Also, the additive amount of uranium absorption agent and comparison adsorbent in the control present invention is 0.67g/L, i.e. uses in every liter of brine
0.67g adsorbent carries out absorption test.
From figure 3, it can be seen that compared to common carbon nanotube, due to introducing amidoxim functional group, uranium of the invention
Adsorbent has been significantly reduced the adsorptive selectivity of other ions；The result further demonstrates uranium absorption of the invention
Agent also indicates that uranium absorption agent of the invention is suitable for complicated water in the presence of competing ions to the special complexing power of uranium
Uranium is effectively adsorbed in body, adsorptive selectivity is good.
Although the present invention has shown and described referring to specific embodiment, it should be appreciated by those skilled in the art that:
In the case where not departing from the spirit and scope of the present invention being defined by the claims and their equivalents, can carry out herein form and
Various change in details.
Claims (10)
1. a kind of uranium absorption agent, which is characterized in that including carbon nanotube and low-temperature plasma graft in the carbon nanotube
Amidoxime group on surface.
2. uranium absorption agent according to claim 1, which is characterized in that the grafting amount of the amidoxime group be 80%~
85%.
3. uranium absorption agent according to claim 1 or 2, which is characterized in that the carbon nanotube is magnetic modified carbon nano tube
Pipe.
4. uranium absorption agent according to claim 3, which is characterized in that the equilibrium adsorption capacity of the uranium absorption agent is 3.8mg/
G~4.1mg/g.
5. a kind of preparation method of uranium absorption agent, which is characterized in that comprising steps of
S1, using Low Temperature Plasma Treating carbon nanotube, obtain amide carbon nano tube；
S2, hydroxylamine hydrochloride alcohol solution is prepared, and its pH is adjusted to neutrality；
S3, the amide carbon nano tube is added into neutral hydroxylamine hydrochloride alcohol solution, reacted at 60 DEG C~80 DEG C to
Few 8h, products therefrom is washed to neutral and dry, obtains uranium absorption agent.
6. preparation method according to claim 5, which is characterized in that in the step S1, the carbon nanotube is magnetic
Property modified carbon nano-tube；It is described magnetism modified carbon nano-tube the preparation method comprises the following steps:
S11, ferric chloride solution is prepared；
S12, unmodified carbon nanotube is added into the ferric chloride solution, and is uniformly dispersed, obtain suspension；
S13, under protective atmosphere, frerrous chloride and ammonium hydroxide are added into the suspension, is back at 60 DEG C~100 DEG C few
1h, it is dry after cooling washing, obtain the magnetic modified carbon nano-tube.
7. preparation method according to claim 6, which is characterized in that in the step S12, in the ferric chloride solution
The mass ratio of iron chloride and the unmodified carbon nanotube is 1.2~2.4:1~2.
8. preparation method according to claim 6, which is characterized in that in the step S13, the frerrous chloride and institute
The mass ratio for stating the unmodified carbon nanotube in suspension is 1~2.5:1~2.
9. according to any preparation method of claim 5-8, which is characterized in that the step S1's method particularly includes:
The carbon nanotube and grafted monomers are mixed, gained mixture is placed in reaction of low temperature plasma device；Wherein, institute
Stating grafted monomers is dimethyl amide or diaminomaleonitrile；The carbon nanotube and the ratio of the dimethyl amide are
The ratio of 1g/400mL~1g/500mL, the carbon nanotube and the diaminomaleonitrile is 1g/50mL~1g/100mL；
Under protective atmosphere, the mixture reacts at least at 200 DEG C~400 DEG C of temperature and the discharge power of 10W~20W
30min obtains the amide carbon nano tube.
10. according to any preparation method of claim 5-8, which is characterized in that in the step S3, the neutrality
The mass ratio of hydroxylamine hydrochloride and amide carbon nano tube in hydroxylamine hydrochloride alcohol solution is 1.1g~2g:0.5g~1g.
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| CN111346620A (en) * | 2018-12-21 | 2020-06-30 | 大庆净达环保科技有限公司 | Modified material with adsorption performance, preparation method and application thereof |
| CN112479166A (en) * | 2020-11-27 | 2021-03-12 | 常熟理工学院 | Method for preparing hydroxylamine hydrochloride by utilizing waste incineration fly ash |
| CN112569914A (en) * | 2020-12-11 | 2021-03-30 | 常熟理工学院 | Method for preparing uranium adsorbent by using ammonia water and acrylonitrile wastewater of coking plant |
| CN114160103A (en) * | 2021-11-24 | 2022-03-11 | 江苏大学 | Preparation method of three-dimensional macroporous amidoximated ionic gel adsorbent |
| CN114433036A (en) * | 2022-01-28 | 2022-05-06 | 江苏大学 | Method for preparing amidoxime functionalized hollow polymer ball based on solvent mixing induction bubble template method and application of amidoxime functionalized hollow polymer ball in uranium extraction |
| CN114643046A (en) * | 2022-02-14 | 2022-06-21 | 江苏大学 | Preparation method of amidoxime microgel adsorbent and application of amidoxime microgel adsorbent in rapid uranium extraction |
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| CN112479166B (en) * | 2020-11-27 | 2023-04-21 | 常熟理工学院 | Method for preparing hydroxylamine hydrochloride by utilizing waste incineration fly ash |
| CN112569914A (en) * | 2020-12-11 | 2021-03-30 | 常熟理工学院 | Method for preparing uranium adsorbent by using ammonia water and acrylonitrile wastewater of coking plant |
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| CN114160103B (en) * | 2021-11-24 | 2023-09-22 | 江苏大学 | Preparation method of three-dimensional large Kong Xiean oximation ion gel adsorbent |
| CN114433036A (en) * | 2022-01-28 | 2022-05-06 | 江苏大学 | Method for preparing amidoxime functionalized hollow polymer ball based on solvent mixing induction bubble template method and application of amidoxime functionalized hollow polymer ball in uranium extraction |
| CN114433036B (en) * | 2022-01-28 | 2024-04-16 | 深圳万知达技术转移中心有限公司 | Method for preparing amidoxime functionalized hollow polymer spheres based on solvent mixing-induced bubble template method and application of amidoxime functionalized hollow polymer spheres in uranium extraction |
| CN114643046A (en) * | 2022-02-14 | 2022-06-21 | 江苏大学 | Preparation method of amidoxime microgel adsorbent and application of amidoxime microgel adsorbent in rapid uranium extraction |
| CN114643046B (en) * | 2022-02-14 | 2024-04-09 | 珠海维迈克建筑安装工程有限公司 | Preparation method of amidoxime microgel adsorbent and application thereof in rapid uranium extraction |
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