CN114984919A - Double amidoxime group-based cellulose adsorbing material and preparation method thereof - Google Patents
Double amidoxime group-based cellulose adsorbing material and preparation method thereof Download PDFInfo
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- CN114984919A CN114984919A CN202210655907.6A CN202210655907A CN114984919A CN 114984919 A CN114984919 A CN 114984919A CN 202210655907 A CN202210655907 A CN 202210655907A CN 114984919 A CN114984919 A CN 114984919A
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- 239000001913 cellulose Substances 0.000 title claims abstract description 61
- 229920002678 cellulose Polymers 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 43
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002244 precipitate Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229920002521 macromolecule Polymers 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 7
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 238000003756 stirring Methods 0.000 claims abstract description 4
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- 239000003463 adsorbent Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 claims description 2
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 claims description 2
- 244000198134 Agave sisalana Species 0.000 claims description 2
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 244000299507 Gossypium hirsutum Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 2
- 240000000249 Morus alba Species 0.000 claims description 2
- 235000008708 Morus alba Nutrition 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 235000014676 Phragmites communis Nutrition 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- DFJYZCUIKPGCSG-UHFFFAOYSA-N decanedinitrile Chemical compound N#CCCCCCCCCC#N DFJYZCUIKPGCSG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 2
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 26
- -1 bisamide oxime Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
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- 238000005265 energy consumption Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/0265—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries extraction by solid resins
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B01J2220/00—Aspects relating to sorbent materials
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- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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Abstract
The invention discloses a dual amidoxime group-based cellulose adsorbing material and a preparation method thereof. Dissolving cellulose-based macromolecular substances in an alkali and urea system solution at a low temperature, and stirring at the low temperature to completely dissolve the cellulose-based macromolecular substances; adding sodium periodate, regulating the pH value with hydrochloric acid, reacting in a constant-temperature and light-proof water bath at a high temperature, centrifugally collecting precipitate, washing and drying to obtain aldehyde cellulose; adding dinitrile substances and piperidine solution, carrying out high-temperature reaction under nitrogen, centrifuging, collecting precipitate, washing and drying to obtain the cyano cellulose; dissolving in organic solvent, adding hydroxylamine hydrochloride and inorganic base to react, centrifuging, collecting precipitate, washing and drying to obtain bisamidoxime cellulose. The bisamide oxime cellulose prepared by the method has high uranium adsorption performance, and the method is simple, rich in raw material quantity, mild in reaction condition and low in energy consumption.
Description
Technical Field
The invention belongs to an adsorbing material in the field of uranium extraction from seawater and a preparation method thereof, and particularly relates to a bisamidoxime group cellulose-based adsorbing material and a preparation method thereof.
Background
In the world, energy demand is rising continuously, global resources are decreasing day by day, nuclear energy is used as clean energy and is an important means for dealing with energy crisis, so the development of uranium resources will also face a serious challenge! The average uranium content in the crust was about 2.5ppm, i.e. about 2.5g uranium per ton of crust material on average, but not high in total. The concentration of uranium in seawater is quite low, and each ton of seawater contains only 3.3mg of uranium on average, but the total amount of the seawater is very large, so that the total content of uranium in the seawater can reach 45 hundred million tons, which is 1000 times of that of the traditional terrestrial uranium ore resource, and can sufficiently meet the sustainable development of human nuclear power generation for thousands of years. And the process of extracting uranium from seawater is very environment-friendly, is completely different from the destructive mining form of the uranium ore on land, can realize the resource mining and environmental protection, and is an environment-friendly and green uranium resource mining technology. Therefore, relevant research work is carried out in the fields of the mechanism of extracting uranium from seawater, the engineering technology of extracting uranium from seawater and the like.
Because of the low uranium concentration (3-4ppb) in seawater, competitive metal ions are present and the wide variety of microorganisms prevents ligand binding to uranium. Therefore, the extraction of uranium from seawater is an exploratory research subject with great difficulty, long period, strong comprehensiveness and wide related range. At present, the main methods for extracting uranium from seawater comprise: adsorption separation, membrane separation, ion exchange, solution extraction, and chemical precipitation.
Chinese patent publication No. CN109847724A discloses a method for preparing a semi-interpenetrating network hydrogel thin film material for extracting uranium from seawater, which comprises dissolving polypropylene amidoxime, a monomer, a photoinitiator and a cross-linking agent in an alkaline aqueous solution according to a certain mass ratio to obtain a precursor solution, and then injecting the precursor solution into a mold for polymerization under ultraviolet rays or sunlight. The preparation method is simple and rapid, and has low cost. The material has the thickness of 0.2mm, uniform micro-pore diameter, high adsorption efficiency, high selectivity, excellent mechanical property and repeated use, but the material has weak hydrophilic property.
Chinese patent document CN108579709A discloses a preparation method of a porous elastic composite material for extracting uranium from seawater, which comprises the following steps: preparing amidoximated polyacrylonitrile solution, mixing with strong alkali water solution, adding into high molecular material water solution, vacuum defoaming, drying, cross-linking and gelating, and rinsing with clear water. The invention improves the coating strength of amidoximated polyacrylonitrile on the porous elastic material framework, improves the flexibility, mechanical stability and hydrophilicity of the material, but the material has low selectivity to uranium ions and has the interference effect of competitive ions.
Chinese patent publication No. CN112920279A discloses a method for preparing an anti-biofouling type polymeric peptide hydrogel material for uranium extraction from seawater, which comprises adding phosphate solution containing polypeptide monomers into a cross-linking agent for polymerization reaction to obtain a hydrogel product, and then freezing and drying to obtain the polymeric peptide hydrogel material. The method has low synthesis temperature and simple process; the prepared polymer peptide hydrogel material has unique spatial structure and coordination elements, good hydrophilicity, high binding affinity, high selectivity and high anti-biological fouling activity, but relatively weak adsorption capacity to uranium.
Chinese patent publication No. CN110256550A discloses a method for preparing a recombinant spidroin fiber material for uranium extraction from seawater: recombining the required gene segments to obtain a uranium extracted from seawater recombinant spidroin protein coding gene, transferring the gene into escherichia coli, carrying out protein expression and purification to obtain a uranium extracted from seawater recombinant spidroin protein liquid, pushing the concentrated uranium extracted from seawater recombinant spidroin protein liquid into spinning liquid, and carrying out self-assembly to obtain the uranium extracted from seawater recombinant spidroin protein liquid. The method has the advantages of simple process, mild conditions and easy purification, and the uranium extraction from seawater recombinant spider silk protein fiber material prepared by the method has excellent mechanical properties, strong uranium adsorption capacity and high selectivity, and can be repeatedly used. However, the material has high cost, is not easy to recycle and extract and has general antifouling property.
Therefore, the material in the prior art can not keep the adsorption amount of the adsorbent to be relatively high under the conditions of different pH, different temperature and different concentration.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a dual amidoxime group-based cellulose adsorbing material and a preparation method thereof.
The technical scheme of the invention is as follows:
(1) dissolving cellulose-based macromolecular substances in an alkali and urea system solution at low temperature, and violently stirring for 0.1-6 hours at low temperature until the cellulose-based macromolecular substances are completely dissolved to obtain a cellulose solution;
the low temperature is-5-4 ℃.
(2) Adding a certain amount of sodium periodate into a cellulose solution, adjusting the pH value by using 1mol/L hydrochloric acid, reacting in a constant-temperature light-proof water bath at a high temperature, centrifugally collecting the precipitate after the reaction is finished, washing the precipitate with pure water for multiple times to remove impurities, and drying to obtain aldehyde cellulose;
(3) adding the obtained aldehyde cellulose into a single-neck flask, adding dinitrile substances, adding a piperidine solution, reacting at high temperature for 24-48h under the nitrogen atmosphere, centrifuging to collect the lower precipitate, washing the precipitate pure water for multiple times to remove impurities, and drying to obtain the cyano cellulose;
(4) dissolving the obtained cyano cellulose in an organic solvent, then adding a certain amount of hydroxylamine hydrochloride and an inorganic base into the solution, reacting for 1-12 hours at 50-90 ℃, centrifugally collecting the next precipitate after the reaction is finished, washing the precipitate with pure water for many times to remove impurities, and drying to obtain the bisamidoxime cellulose.
The cellulose-based macromolecular substance is at least one of cellulose powder, microcrystalline cellulose, ethyl cellulose, reed, sisal, straw, bagasse, cotton, flax and mulberry twig bark;
the alkali in the alkali/urea system is at least one of sodium hydroxide, potassium hydroxide, aluminum hydroxide, calcium hydroxide and lithium hydroxide.
In the step (2): the mass of the sodium periodate accounts for 0.5-5% of the total mass of the cellulose solution and the sodium periodate, and the pH range is adjusted to 4-8.
In the step (2): the high temperature is 50-100 ℃, the reaction time is 2-12h, and the centrifugal speed is 8000-.
In the step (3): the dinitrile substance is at least one of malononitrile, succinonitrile, adiponitrile, sebaconitrile, tetrafluoroterephthalonitrile and diaminomaleonitrile.
In the step (3): the concentration of the piperidine solution is 0.1-1g/L, and the high temperature condition is 80-140 ℃.
In the step (4): the mass of the cyano-cellulose accounts for 5-15% of the total mass of the mixed system of the cyano-cellulose and the organic solvent, and the mass ratio of the cyano-cellulose to the hydroxylamine hydrochloride to the inorganic base is 5: 6: 3.
in the step (4): the organic solvent is at least one of N, -N dimethylacetamide, N, -N dimethylformamide and dimethyl sulfoxide, and the inorganic base is at least one of sodium hydroxide, aluminum hydroxide, zinc hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
The invention has the beneficial effects that:
(1) the required raw materials are rich in variety, the base material sources are wide, and the cost is low.
(2) Under the conditions of different pH values, different temperatures and different concentrations, the uranium adsorbent has a good uranium adsorption effect.
(3) The adsorbing material prepared by the method has huge application prospect in the fields of uranium extraction from seawater, industrial wastewater recovery treatment, heavy metal recovery, radioactive sewage treatment, environmental remediation and the like.
In conclusion, the bisamidoxime cellulose prepared by the method has high uranium adsorption performance, and the method is simple, rich in raw material, mild in reaction conditions and low in energy consumption.
Drawings
FIG. 1 is a graph comparing the adsorption capacity results of examples 2 to 6 at different pH;
FIG. 2 is a graph comparing the results of adsorption amounts for examples 7-11 at different temperatures;
FIG. 3 is a graph comparing the results of adsorption amounts of examples 12 to 14 at different uranyl nitrate concentrations.
Detailed Description
The present invention is described in more detail by the following examples, which are not intended to limit the present invention.
The embodiments of the invention are as follows:
example 1:
(1) 2g of cellulose powder was dissolved in 60mL of an alkali and urea system solution at a low temperature of-5 ℃ and maintained at the low temperature, followed by vigorous stirring for 4 hours until the cellulose powder was completely dissolved.
(2) Adding 2g of sodium periodate into the cellulose solution dissolved in the step (1), adjusting the pH value to 4 by using 1mol/L hydrochloric acid, reacting in a water bath at the constant temperature of 60 ℃ in a dark condition, after the reaction is finished, placing the obtained product into a centrifuge at 8000RPM for centrifuging for 5 minutes, collecting the precipitate, washing the precipitate with pure water for multiple times to remove impurities, and freeze-drying to obtain the aldehyde cellulose.
(3) Adding the prepared aldehyde cellulose into a single-neck flask, adding malononitrile, adding a piperidine solution, reacting at the high temperature of 80 ℃ for 48 hours under the nitrogen atmosphere, centrifuging, collecting the precipitate below, washing the precipitate with pure water for multiple times to remove impurities, and drying to obtain the cyano cellulose.
(4) Dissolving the cyano cellulose obtained in the step (3) in an organic solvent N, -N dimethylformamide, then adding a certain amount of hydroxylamine hydrochloride and sodium hydroxide into the solution, reacting for 12 hours at the high temperature of 80 ℃, centrifuging and collecting the next precipitate after the reaction is finished, washing the precipitate with pure water for many times to remove impurities, and drying to obtain the bisamido cellulose.
(5) Preparing 100mL of 500mg/L uranyl nitrate solution, measuring 10mL of uranyl nitrate solution, diluting the uranyl nitrate solution to 100mg/L, adjusting the pH to 4 by using 1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide solution, weighing 5mg of bisamidoxime cellulose, adding the bisamidoxime cellulose into 50mL of 100mg/L uranyl nitrate solution with the pH to 4, adsorbing the mixture for 24 hours at the temperature of 20 ℃ at 180RPM in a water bath oscillator, and measuring the uranium ion concentration by using an azoarsine photometry.
The adsorption capacity of the cellulose-based amidoximation uranium extraction microsphere prepared by the method is an important parameter for evaluating the adsorption performance of the cellulose-based amidoximation uranium extraction microsphere. Wherein the adsorption capacity is defined as:
wherein, C 0 Representing the initial concentration of the uranium content in the uranyl nitrate solution; c t Represents the concentration at which adsorption reaches time t; v represents the volume of the uranyl nitrate solution; m (g) is the mass of added adsorbent; and q represents the uranium adsorption amount of the sample to the uranium-containing solution at the reaction time t.
Examples 2 to 6:
adjusting the pH of the uranyl nitrate solution of 100mg/L to 5, 6, 7, 8 and 9 respectively by using 1mol/L hydrochloric acid and 1mol/L sodium hydroxide solution. The adsorption amounts at different pH were obtained and the results are shown in fig. 1. As can be seen from fig. 1, the adsorption amount of the adsorbent tends to increase and decrease with increasing pH, and the adsorbent reaches the maximum adsorption amount at pH 6, and thus it is known that the optimum adsorption pH of the adsorbent is 6.
Examples 7 to 11:
5mg of bisamidoxime-based cellulose is weighed and added into 50mL uranyl nitrate solution with the pH value of 6 and the concentration of 100mg/L, the uranyl nitrate solution is adsorbed for 24 hours under the conditions of 180RPM of a water bath oscillator at the temperature of 20 ℃, 40 ℃, 60 ℃ and 80 ℃, the uranium ion concentration is measured by an azoarsine spectrophotometry, and the adsorption amount at different temperatures is calculated, and the result is shown in figure 2. As can be seen in fig. 2, the adsorption amount of the adsorbent increases with increasing temperature under the optimum pH condition. From this, it is understood that the adsorbent has a higher adsorption capacity as the temperature is higher, without changing other conditions.
Examples 12 to 14:
weighing 5mg of bisamidoxime cellulose, adding the bisamidoxime cellulose into 50mL of uranyl nitrate solution with the pH value of 6, adsorbing the bisamidoxime cellulose for 24 hours under the conditions of the uranyl nitrate concentration of 50mg/L, 100mg/L, 150mg/L and the like at 180RPM of a water bath oscillator, measuring the uranium ion concentration by an azoarsine photometry, and calculating the adsorption amount under different concentrations, wherein the result is shown in figure 3. As can be seen in fig. 3, at the optimum pH, the adsorption amount increases with increasing uranyl nitrate concentration, and the increase is large. It is found that the higher the concentration, the higher the utilization efficiency of the adsorbent functional group, and the larger the adsorption amount.
Claims (10)
1. A preparation method of a double amidoxime group-based cellulose adsorbing material is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving cellulose-based macromolecular substances in an alkali and urea system solution at a low temperature, and violently stirring for 0.1-6 hours at the low temperature until the cellulose macromolecular substances are completely dissolved to obtain a cellulose solution;
(2) adding a certain amount of sodium periodate into a cellulose solution, adjusting the pH value by using hydrochloric acid, reacting in a constant-temperature light-proof water bath at a high temperature, centrifugally collecting the precipitate after the reaction is finished, washing the precipitate with pure water for many times to remove impurities, and drying to obtain aldehyde cellulose;
(3) adding the obtained aldehyde cellulose into a single-neck flask, adding dinitrile substances, adding a piperidine solution, reacting at high temperature for 24-48h under the nitrogen atmosphere, centrifuging to collect the lower precipitate, washing the precipitate pure water for multiple times to remove impurities, and drying to obtain the cyano cellulose;
(4) dissolving the obtained cyano cellulose in an organic solvent, then adding a certain amount of hydroxylamine hydrochloride and an inorganic base, reacting for 1-12 hours at 50-90 ℃, centrifugally collecting the next precipitate after the reaction is finished, washing the precipitate with pure water for many times to remove impurities, and drying to obtain the bisamido cellulose.
2. The method for preparing a bis-amidoxime-based cellulose adsorbing material according to claim 1, wherein the method comprises the following steps: the cellulose-based macromolecular substance is at least one of cellulose powder, microcrystalline cellulose, ethyl cellulose, reed, sisal, straw, bagasse, cotton, flax and mulberry twig bark;
the alkali in the alkali/urea system is at least one of sodium hydroxide, potassium hydroxide, aluminum hydroxide, calcium hydroxide and lithium hydroxide.
3. The method for preparing a bis-amidoxime-based cellulose adsorbing material according to claim 1, wherein the method comprises the following steps: in the step (2): the mass of the sodium periodate accounts for 0.5-5% of the total mass of the cellulose solution and the sodium periodate, and the pH range is adjusted to 4-8.
4. The method for preparing a bis-amidoxime-based cellulose adsorbing material according to claim 1, wherein the method comprises the following steps: in the step (2): the high temperature is 50-100 ℃, the reaction time is 2-12h, and the centrifugal speed is 8000-14000 RPM.
5. The method for preparing a bis-amidoxime-based cellulose adsorbing material according to claim 1, wherein the method comprises the following steps: in the step (3): the dinitrile material is at least one of malononitrile, succinonitrile, adiponitrile, sebaconitrile, tetrafluoroterephthalonitrile and diaminomaleonitrile.
6. The method for preparing a bis-amidoxime-based cellulose adsorbing material according to claim 1, wherein the method comprises the following steps: in the step (3): the concentration of the piperidine solution is 0.1-1g/L, and the high temperature condition is 80-140 ℃.
7. The method for preparing a bis amidoxime based cellulose adsorbent material according to claim 1, wherein: in the step (4): the mass of the cyano-cellulose accounts for 5-15% of the total mass of the cyano-cellulose and organic solvent mixed system, and the mass ratio of the cyano-cellulose to the hydroxylamine hydrochloride to the inorganic base is 5: 6: 3.
8. the method for preparing a bis-amidoxime-based cellulose adsorbing material according to claim 1, wherein the method comprises the following steps: in the step (4): the organic solvent is at least one of N, -N dimethylacetamide, N, -N dimethylformamide and dimethyl sulfoxide, and the inorganic base is at least one of sodium hydroxide, aluminum hydroxide, zinc hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
9. Bisamidoxime based cellulose adsorbing material characterized in that it is obtained by the process according to any one of claims 1 to 8.
10. Use of a bis amidoxime based cellulose adsorbing material according to claim 9, wherein: the application in extracting uranium from seawater.
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