CN105709703A - Reparation and application of chelating resin and mercury ion detection method - Google Patents

Reparation and application of chelating resin and mercury ion detection method Download PDF

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CN105709703A
CN105709703A CN201610068961.5A CN201610068961A CN105709703A CN 105709703 A CN105709703 A CN 105709703A CN 201610068961 A CN201610068961 A CN 201610068961A CN 105709703 A CN105709703 A CN 105709703A
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chelating resin
chlorine ball
resin
preparation
mercury ion
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童再再
徐海岸
张祥
熊春华
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/02—Food
    • G01N33/14—Beverages
    • G01N33/146—Beverages containing alcohol

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  • Treatment Of Water By Ion Exchange (AREA)

Abstract

The invention provides preparation and application of chelating resin and a mercury ion detection method. The preparation method of the chelating resin includes the following steps that 1, a chlorine ball is soaked in an N,N-dimethyl formamide serving as a reaction solvent till the chlorine ball fully swells; 2, N-methyl thiourea serving as a ligand and sodium serving as a catalyst are added to the product obtained in the step 1, stirring reaction is performed at the temperature of 85-95 DEG C under the condition of nitrogen protection for 10-14 hours, wherein the mass ratio of the N-methyl thiourea to -CH2Cl substance in the chloride ball is (3-5): (1); 3, the product obtained in the step 2 is filtered to obtain a filter cake, the filter cake is first soaked and washed with a reaction solvent till a washing solution is colorless, then is washed with distilled water, further is washed with anhydrous ethanol, acetone, ether and distilled water sequentially for several times and is subjected to vacuum drying at the temperature of 45-55 DEG C to obtain the chelating resin. The prepared chelating resin has the advantages of having the good effect of separating mercury ions in baijiu, strong anti-interference performance, low detection cost and the like.

Description

The preparation of a kind of chelating resin and application and the detection method for mercury ion
Technical field
The present invention relates to the preparation of a kind of chelating resin and application and the detection method for mercury ion, especially a kind of dialogue In wine, mercury ion has that good separating effect, strong interference immunity, testing cost be low, the preparation of the novel chelate resin of repeatable utilization And apply and detection method, belong to synthetic method and the performance study field of chelating adsorption function resin.
Background technology
Industrial expansion, the progress of science and technology, promote developing rapidly of economy, improve the quality of people's lives, but to the mankind The environment depended on for existence causes threat greatly.The polluter of heavy metal is mainly industrial pollution, living garbage pollution and friendship Logical pollution, in nature, a lot of organic compound can make it poison reduction by auto-degradation, and heavy metal element has enrichment Property, it is difficult in the environment degrade.By to soil, water body, the pollution of air, heavy metal can be enriched to cereal crops, Aquatic product In the food closely-related with the mankind such as product, by food chain constantly to being in mankind's cylinder accumulation on top, and then the harm mankind Healthy.It is mainly manifested in the feature of food pollution that disguise, toxicity is big, amplification and trace.Therefore, to food In product, trace heavy metal element content is analyzed measuring, and controls content of heavy metal in foods, formulates survey unified, easily and effectively Determine method and ensure that Safety of Food Quality is extremely the most urgent.
Chinese liquor is one of six big Spirits in the world, in state-owned long developing history, cereal crops brewage and form, promote The development of food industry and national economy.During wine brewing, cereal crops growing environment, brewing process and Chinese liquor exist Storing and be likely to be polluted by heavy metal in transportation, therefore, in detection Chinese liquor, whether heavy metal exceeds standard the most necessary.
Chelating resin refers to that the class containing the functional group that can form chelate with metal ion is resinoid high polymer.Function Group also exists the atoms such as O, N, S, P, the As with non-bonding lone pair electrons, these atomic energys with a pair lone pair electrons with Metal ion forms coordinate bond, constitutes the rock-steady structure similar to little molecule chelate.The mechanism of adsorbing metal ions is on resin Function atom and metal ion generation complexation reaction, form the rock-steady structure that similar little molecule chelate is similar.Chelating resin Preparation typically utilizes the natural or parent of synthetic, is introduced wherein by the side base with chelating function by chemical reaction.Compare In by the monomer containing chelating function base through the processing extractant produced of polymerization, the chelating resin that this method prepares is economical, The advantage of the aspects such as high selectivity, the most more application prospect.
Summary of the invention
In order to solve above-mentioned technical problem, the present invention provides a kind of to mercury ion good separating effect, strong interference immunity, inspection in Chinese liquor Survey low cost, the preparation of chelating resin of repeatable utilization and application and the detection method for mercury ion.
In order to reach above-mentioned technical purpose, the present invention provides the preparation method of a kind of chelating resin, the method with chlorine ball as parent, N-methylthiourea is part, is modified the benzyl on chlorine ball, and described chlorine ball is that macroporous type chloroethyl crosslinked polystyrene is micro- Ball；Described preparation method comprises the following steps:
1) chlorine ball is immersed in the DMF of reaction dissolvent, until chlorine ball is the most swelling；
2) in step 1) gains in add the N-methylthiourea as part and the sodium as catalyst, nitrogen protect Under conditions of protecting, at 85-95 DEG C, stirring is reacted 10-14 hour；Described N-methylthiourea and-CH in chlorine ball2The ratio of the amount of Cl material For 3-5:1；Preferably: under conditions of nitrogen is protected, at 90 DEG C, stirring is reacted 12 hours；Described N-methylthiourea and chlorine -CH in ball2The ratio of the amount of Cl material is 4:1；
3) filtration step 2) gains obtain filter cake；It is first colourless, then by filter cake reaction dissolvent washing by soaking to cleaning mixture With distilled water wash, more successively with dehydrated alcohol, acetone, ether and distilled water wash for several times, 45-55 DEG C of vacuum drying, obtain Chelating resin；Preferably 50 DEG C vacuum drying.
As preferably: described step 1) in: chlorine ball with the amount ratio of N,N-dimethylformamide is: 1mg chlorine ball: 0.5～1mL DMF, soak time is 22～26 hours；Preferably: 1mg chlorine ball: the N of 0.8mL, N-dimethyl Methanamide, soak time is 24 hours；
Described step 2) in, speed of agitator is 250-350r/min；Preferably: speed of agitator is 300r/min.
The application of the chelating resin that a kind of method prepared as described above prepares, this application mainly comprises the steps that
1) in the chelating resin of preparation, add the NaAc_HAc buffer solution of pH=4.0, and soak 22-26h, preferably 24h；
2) in step 1) gains in add mercury ion titer, in temperature 30-40 DEG C, the perseverance of rotating speed 140-160r/min Temperature agitator vibrates；Wherein chelating resin with the amount ratio of mercury ion standard solution is: 12-18mg chelating resin: 25ml hydrargyrum Ion standard solution；Preferably: temperature 35 DEG C, rotating speed 150r/min constant temperature oscillator in vibrate；Wherein chelating resin With the amount ratio of mercury ion standard solution it is: 15mg chelating resin: 25ml mercury ion standard solution；
3) chelating resin saturated adsorption capacity to cadmium ion is measured after balance upon adsorption.
The chelating resin that a kind of method prepared as described above prepares is for the detection method of mercury ion, and this detection method includes following step Rapid:
(1) pre-treatment of testing sample: testing sample is preprocessed, micro-wave digestion, after cooling, obtain containing mercuric to be measured Solution；
(2) separation and preconcentration of chelating resin: solution to be measured regulation is placed on to pH=4.0 the dynamic adsorption post of chelating resin In, coutroi velocity is that 1.5-2.5mL/min passes through, and after dynamic adsorption terminates, adds strippant, with the stream of 0.5-1.5mL/min Speed carries out desorbing by described dynamic adsorption post, and detects outflow solution concentration, it is preferred that coutroi velocity is 2.0mL/min Pass through, after dynamic adsorption terminates, add strippant, carry out desorbing with the flow velocity of 1mL/min by described dynamic adsorption post
5, chelating resin according to claim 4 is for the detection method of mercury ion, it is characterised in that described step (2) In the HNO that strippant is 25-35mL 4mol/L3The mixed liquor of hydrochloric acid；Described testing sample is Chinese liquor, it is preferred that solve Vapor is the HNO of 30mL 4mol/L3The mixed liquor of hydrochloric acid.
Use the novel chelate resin that is prepared of the inventive method also can carry out following specific experiment:
1) mercury ion adsorption experiment:
Weighing a certain amount of resin to be placed in iodine flask, the buffer solution adding different pH soaks 24h, is subsequently adding heavy metal Ion titer, constant temperature shaking in constant temperature oscillator, measure residual metal ions in analysis aqueous phase at regular intervals with ICP Concentration, until balance.Adsorbance (q is calculated with following formulae) and distribution ratio (D):
Q e = ( C o - C e ) V m
D = Q e C e
Q in formulaeEquilibrium adsorption capacity (mg/g) for resin；CoAnd CeIt is respectively the initial concentration (mg/mL) of metal ion in aqueous phase With equilibrium concentration (mg/mL)；M is resin quality (g)；V0For metal ion solution volume (mL).
2) desorption experiment:
Being washed with deionized repeatedly by the resin after adsorption equilibrium, add a certain amount of strippant after drying, constant temperature oscillation is to flat The concentration of mercury ion in solution is measured after weighing apparatus.Desorption efficiency E (%) is calculated as follows:
E ( % ) = ( C d V d ) ( C 0 - C e ) V × 100 %
C in formuladFor the equilibrium concentration (mg/mL) of metal ion in stripping liquid；VdFor stripping liquid volume (mL).C0、CeAnd V0Ibid. Resin after desorbing is reused for heavy metal adsorption, and every kind of resin carries out 5 adsorption-desorption cyclic processes.
The present invention is directed in Chinese liquor complicated system (containing other ions multiple), in conjunction with metal ion valence shell structure with The spatial coordination effect of part and electronic effect, realize the most theoretical screening to target ligand by the calculating sifting of quantum chemistry, Then go out a series of synthetic route according to the ligand design picked out, and be modified.
The present invention, relative to prior art, has the advantage that
1) the raw material chlorine ball of the novel chelate resin that the present invention prepares has higher mechanical strength and physical stability, and originates Extensively, cheap, production cost is low, has obvious economic benefit；
2) present invention utilizes chemical graft process by chlorine ball modification so that it is have a bigger chemical stability, and enhance opposing acid, Alkali and the ability of organic solvent and absorbability thereof, and there is good desorption performance and recycling rate of waterused is high, there is obvious ring Guarantor, economic benefit；
3) novel chelate resin that the present invention prepares is to hydrargyrum (Hg2+) there is higher adsorptive selectivity, and the rate of adsorption is fast, inhales Attached equilibration time is short；
4) preparation method of the novel chelate resin of the present invention is easy and simple to handle, and productivity is high；
5) novel chelate resin prepared by the present invention Hg ion detection in Chinese liquor is had good separating effect, capacity of resisting disturbance strong, The features such as testing cost is low.
Accompanying drawing explanation
Fig. 1 is the reaction principle figure of the present invention；
Fig. 2 is the reaction mol ratio impact on chlorine ball function base conversion ratio；
Fig. 3 is the reaction temperature impact on chlorine ball function base conversion ratio；
Fig. 4 is the novel chelate resin impact on the adsorption capacity of metal ion Hg (II) under different pH value.
Detailed description of the invention
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in further detail.Shown in Fig. 1, one of the present invention The preparation method of chelating resin, the method is with chlorine ball as parent, and N-methylthiourea is part, is modified the benzyl on chlorine ball, Described chlorine ball is macroporous type chloroethyl crosslinked polystyrene microsphere；Described preparation method comprises the following steps:
1) chlorine ball is immersed in the DMF of reaction dissolvent, until chlorine ball is the most swelling；
2) in step 1) gains in add the N-methylthiourea as part and the sodium as catalyst, nitrogen protect Under conditions of protecting, at 85-95 DEG C, stirring is reacted 10-14 hour；Described N-methylthiourea and-CH in chlorine ball2The ratio of the amount of Cl material For 3-5:1；Preferably: under conditions of nitrogen is protected, at 90 DEG C, stirring is reacted 12 hours；Described N-methylthiourea and chlorine -CH in ball2The ratio of the amount of Cl material is 4:1；
3) filtration step 2) gains obtain filter cake；It is first colourless, then by filter cake reaction dissolvent washing by soaking to cleaning mixture With distilled water wash, more successively with dehydrated alcohol, acetone, ether and distilled water wash for several times, 45-55 DEG C of vacuum drying, obtain Chelating resin；Preferably 50 DEG C vacuum drying.
As preferably: described step 1) in: chlorine ball with the amount ratio of N,N-dimethylformamide is: 1mg chlorine ball: 0.5～1mL DMF, soak time is 22～26 hours；Preferably: 1mg chlorine ball: the N of 0.8mL, N-dimethyl Methanamide, soak time is 24 hours；
Described step 2) in, speed of agitator is 250-350r/min；Preferably: speed of agitator is 300r/min.
The application of the chelating resin that a kind of method prepared as described above prepares, this application mainly comprises the steps that
1) in the chelating resin of preparation, add the NaAc_HAc buffer solution of pH=4.0, and soak 22-26h, preferably 24h；
2) in step 1) gains in add mercury ion titer, in temperature 30-40 DEG C, the perseverance of rotating speed 140-160r/min Temperature agitator vibrates；Wherein chelating resin with the amount ratio of mercury ion standard solution is: 12-18mg chelating resin: 25ml hydrargyrum Ion standard solution；Preferably:, temperature 35 DEG C, rotating speed 150r/min constant temperature oscillator in vibrate；Wherein chelate tree Fat with the amount ratio of mercury ion standard solution is: 15mg chelating resin: 25ml mercury ion standard solution；
3) chelating resin saturated adsorption capacity to cadmium ion is measured after balance upon adsorption.
The chelating resin that a kind of method prepared as described above prepares is for the detection method of mercury ion, and this detection method includes following step Rapid:
(1) pre-treatment of testing sample: testing sample is preprocessed, micro-wave digestion, after cooling, obtain containing mercuric to be measured Solution；
(2) separation and preconcentration of chelating resin: solution to be measured regulation is placed on to pH=4.0 the dynamic adsorption post of chelating resin In, coutroi velocity is that 1.5-2.5mL/min passes through, and after dynamic adsorption terminates, adds strippant, with the stream of 0.5-1.5ml/min Speed carries out desorbing by described dynamic adsorption post, and detects outflow solution concentration, it is preferred that coutroi velocity is 2.0mL/min Pass through, after dynamic adsorption terminates, add strippant, carry out desorbing with the flow velocity of 1ml/min by described dynamic adsorption post
5, chelating resin according to claim 4 is for the detection method of mercury ion, it is characterised in that described step (2) In the HNO that strippant is 25-35mL 4mol/L3The mixed liquor of hydrochloric acid；Described testing sample is Chinese liquor, it is preferred that solve Vapor is the HNO of 30mL 4mol/L3The mixed liquor of hydrochloric acid.
Embodiment 1:
1), accurately weigh 60.0mg chlorine ball, move in the three-necked bottle of 100mL, add 40mL DMF (DMF) soaked overnight, until chlorine ball is swelling；
2), in step 1) gains in add the N-methylthiourea as part, under the protective condition of nitrogen add sodium conduct Catalyst also keeps the reaction temperature of 90 DEG C to stir (rotating speed is 300r/min) reacting 12 hours, wherein, N-methylthiourea and chlorine -CH on ball2The ratio of the amount of the material of Cl is 4:1；
3), reaction terminate after by step 2) gains carry out being filtrated to get filter cake, the filter cake DMF of gained (DMF) washing by soaking 3～4 times (each consumption is 40mL), the most successively with distilled water, dehydrated alcohol, acetone, ether, Distilled water wash, 4 times repeatedly (every time, the consumption of distilled water is 40ml, the consumption of acetone is 40mL, the consumption of ether is 40mL, The consumption of dehydrated alcohol is 40mL)；50 DEG C are dried under vacuum to constant weight, obtain novel chelate resin.
Wherein, chlorine ball be macroporous type chloroethyl crosslinked polystyrene microsphere (also name macroporous type chloroethyl crosslinked polystyrene, PS-CH2Cl, hereinafter referred to as chlorine ball), such as it is purchased from Chemical Plant of Nankai Univ. etc., the degree of cross linking 6%.
Experiment 1: accurately weigh every part of 4 parts of chlorine ball for 20.0mg and be respectively placed in 100mL iodine flask, be separately added into 30mL DMF soak and within 24 hours, make chlorine ball the most swelling, then be separately added into a certain amount of N-methylthiourea as part (N-methyl sulfur Urea and the-CH in chlorine ball2The ratio of the material amount of Cl is respectively 2:1,3:1,4:1,5:1) and catalyst sodium, protect at nitrogen Under the conditions of at 90 DEG C stirring reaction 12 hours.After reaction terminates, the filter cake of gained is with DMF (DMF) Washing by soaking 3～4 times (each consumption is 40mL), the most successively with distilled water, dehydrated alcohol, acetone, ether, distillation Water washs, 4 times repeatedly (every time, the consumption of distilled water is 40mL, the consumption of acetone is 40mL, the consumption of ether is 40mL, The consumption of dehydrated alcohol is 40mL), 50 DEG C are dried under vacuum to constant weight, obtain novel chelate resin.
According to following formula computing function base conversion ratio, draw the optimum synthesis condition of the chelating resin of the present invention.Function base conversion ratio is pressed Following formula calculates:
N % = 1 × aM N F 0 x 1000 + 1 × F 0 Δ M x
Resin nitrogen content after N% is the synthesis that elementary analysis records in formula, a is the number Han atom N in per molecule part；MNFor atom N Molal weight；F0(5.39mmol/g) it is chlorine ball function base (-CH2Cl) content；Δ M is resin weightening finish after 1mol function base converts Amount (g/mol)；X is the function base conversion ratio of resin.
The result of this experiment is as shown in Figure 2.Learn according to Fig. 2: when mol ratio is relatively low, the function base conversion ratio of resin with mole The rising of ratio and increase；But along with the continuation of mol ratio increases, resin function base conversion ratio but presents downward trend, and this is probably Reaching saturation owing to the avtive spot of parent has been fully contacted with part, also being difficult to improve function base so continuing to improve concentration Conversion ratio.So, finally determine that the optimum response mol ratio of novel chelate resin is 4:1；In i.e. N-methylthiourea and chlorine ball -CH2The ratio most preferably 4:1 of the amount of the material of Cl.
Experiment 2: accurately weigh every part of 5 parts of chlorine ball for 20.0mg and be respectively placed in 100mL iodine flask, be separately added into the DMF of 30mL Soak and within 24 hours, make chlorine ball the most swelling, then be separately added into a certain amount of N-methylthiourea as part (N-methylthiourea and chlorine ball In-CH2The ratio of the amount of the material of Cl is 4:1), under nitrogen protective condition respectively 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, Stirring reaction 12 hours at 120 DEG C.After reaction terminates, being leached by resin, the filter cake of gained is with DMF (DMF) Washing by soaking 3～4 times (each consumption is 40mL), the most successively with distilled water, dehydrated alcohol, acetone, ether, distilled water Washing, 4 times repeatedly (every time, the consumption of distilled water is 40mL, the consumption of acetone is 40mL, the consumption of ether is 40mL, anhydrous The consumption of ethanol is 40mL), 50 DEG C are dried under vacuum to constant weight, obtain novel chelate resin.
Wherein, the calculation of function base conversion ratio is with reference to experiment 1.
The result of this experiment is as shown in Figure 3.According to Fig. 3, learn: when reaction temperature is relatively low, the conversion ratio of resin function base with The rising of temperature and raise；But after reaching certain temperature, continue to rise a high-temperature and can not continue to significantly improve the conversion ratio of function base. Comprehensive Experiment condition and the consideration of combined coefficient, finally determine that the optimum synthesising temperature of novel chelate resin is 90 DEG C.
Experiment 3: accurately weigh novel chelate resin that every part is 15.0mg (prepared according to method as described in embodiment 1 Novel chelate resin) 7 parts be placed in 100mL iodine flask, respectively correspondence add 25mL pH=3.0, pH=3.5, pH=4.0, After the HAc-NaAc buffer solution of pH=4.5, pH=5.0, pH=5.5, pH=6.0 soaks 24 hours, every part adds 5.0mL1mg/mL Mercury ion standard solution, be placed in constant temperature oscillator under 298K, shake with the rotating speed constant temperature of 150r/min, Mei Geyi Mensuration of fixing time analyzes residual metal ions concentration in aqueous phase, until balance.As stated above, can show that pH is to novel chelating tree The fat impact on silver ion absorption property, acquired results is as shown in Figure 4.
Learn according to Fig. 4: chelating resin is 4.0 to the optimal adsorption pH value of Hg (II) solion.
Experiment 4: accurately weigh novel chelate resin that every part is 15.0mg (prepared according to method as described in embodiment 1 Novel chelate resin) 3 parts, every part of mercury ion solution 5mL adding 0.700mg/ml, HAc-NaAc buffer solution (pH is 4.0) 25mL, cumulative volume is 30mL, and in 25 DEG C, vibration absorption under the rotating speed of 300r/min, after adsorption equilibrium；By resin filter, (every time, the consumption of HAc-NaAc is 40mL, distillation to wash 3 times successively with HAc-NaAc (pH is 4.0), distilled water respectively The consumption of water is 40mL), add the stripping liquid that 30mL concentration is different, Hg ion concentration is surveyed in desorbing the most afterwards.
Desorption efficiency E (%) is calculated as follows:
E ( % ) = ( C d V d ) ( C 0 - C e ) V × 100 %
C in formuladFor the equilibrium concentration (mg/mL) of metal ion in stripping liquid；VdFor stripping liquid volume (mL).CoAnd CeIt is respectively aqueous phase The initial concentration (mg/mL) of middle metal ion and equilibrium concentration (mg/mL)；V is mercury ion liquor capacity (mL).Acquired results such as table Shown in 1.
The different strippant impact on Hg (II) desorption efficiency of table 1
Can be obtained by table 1: when being not added with thiourea, desorption efficiency increases along with the concentration of hydrochloric acid and nitric acid and increases, and when nitric acid is dense When degree reaches 4M, desorption efficiency is up to 100%；When thiourea concentration is the same, the concentration of hydrochloric acid increases, and desorption efficiency has the trend of reduction. As shown in Table 1, optimum solution vapor is 4M salpeter solution, and its desorption efficiency may be up to 100%.
Experiment five: accurately weigh novel chelate resin that every part is 100.0mg (prepared according to method as described in embodiment 1 Novel chelate resin) 2 parts, fill post.Weigh six parts of 0.5g Chinese liquor respectively in digestion container, successively add 5mL nitric acid (point Analyse pure) and 2mL 30%H2O2, arranging maximum temperature is 200 DEG C, and maximum pressure is 1096kpa, clears up in microwave dissolver 45min.With the speed of 2mL/min, the Chinese liquor sample liquid after micro-wave digestion is crossed post to adsorb.Then with 4M salpeter solution incited somebody to action Resin after post absorption carries out desorbing, and takes the stripping workshop of 0.1mL respectively in the color comparison tube of 25mL.Add in color comparison tube 4-(2-pyridylazo) the resorcinol developer (PAR) of 1mL 0.1%, and the HAc-NaAc buffering of 10mL pH=4.0 Solution, after distilled water constant volume to 25mL, carries out the detection by quantitative of ultraviolet spectrophotometry, and acquired results can be shown in Table 5.
Comparative example 1: N,N-dimethylformamide (DMF) as solvent in embodiment 1 is made into respectively 1,4-dioxane, Distilled water and toluene, remaining is with embodiment 1.
The three of gained kinds of resins are detected according to above-mentioned experimental technique respectively, the nitrogen content of gained such as table 2.
The nitrogen content of resin prepared by table 2 different solvents
As shown in Table 2, the nitrogen content according to the novel chelate resin of embodiment 1 preparation is the highest.Therefore, novel chelate resin is prepared Optimum response solvent be DMF.
Comparative example 2: the catalyst sodium in embodiment 1 is changed into without, the other the same as in Example 1.Obtained resin is according to upper Stating experimental technique to detect, the nitrogen content of gained is 1.21%.
Comparative example 3: the resin part in embodiment 1 is changed into adenine of the prior art, 2-sulfydryl-1,3,4-thiadiazoles, Thiosemicarbazides, 2-amido-1,3,4-thiadiazoles, phenol and triethylene amine, remaining is with example 1.
The three of gained kinds of resins are detected according to above-mentioned experimental technique respectively, its adsorbance such as table 3 to hydrargyrum.
Table 3 different ligands adsorbance to mercury ion
Part Conversion ratio (%) Adsorbance Q (mg/g)
N-methylthiourea 97.0 347
Adenine 71.3 384
2-sulfydryl-1,3,4-thiadiazoles 91.6 343
Thiosemicarbazides 21.2 56.7
2-amino-1,3,4-thiadiazoles 15.6 81.1
Phenol and triethylene amine 18.6 101.3
2-chloromethyl benzimidazole 6.2 32.3
Comparative example 4: changing the chlorine ball in comparative example 3 into the degree of cross linking is 8%, and remaining is with comparative example 3.Obtained by resin according to Above-mentioned experimental technique detects, and the adsorbance of the mercury ion recorded is 256mg/g.
Comparative example 5: pH in experiment 3 is set as 4.0, being respectively adopted can in the novel chelate resin absorption Chinese liquor of embodiment 1 preparation Heavy metal ion Hg (II) that can contain, Cd (II), Cr (II I), Pb (IV), remaining is with experiment 3.Each metal biosorption Amount is such as table 4.
Table 4 different resins is to metal biosorption amount
Wherein adenine chelating resin takes from patent: wherein number of patent application is 201510059090.6；2-sulfydryl-1,3,4-thiophene Diazole chelating resin takes from patent: wherein number of patent application is 201510058585.7；Phenol/triethylene tetramine chelating resin takes From patent: wherein number of patent application is 201310665564.2.
As shown in Table 4, compared to existing adenine chelating resin and 2-sulfydryl-1,3,4-thiadiazoles chelating resins, the present invention The N-methylthiourea chelating resin provided has higher adsorptive selectivity to mercury ion.
Comparative example 6: make the resin in experiment five into of the prior art and adenine chelating resin and 2-sulfydryl-1,3,4-thiophene two Azoles chelating resin, remaining is with experiment five.The stripping liquid ICP processed in experiment five is detected content of beary metal, with experiment simultaneously Five contrast, its result such as table 5.
Mercury ion in Chinese liquor is adsorbed detection by table 5.N-methylthiourea chelating resin
The content of hydrargyrum in Chinese liquor is the most clearly defined by country's limit standard, but general Chinese liquor is to be made by Semen Tritici aestivi and Fructus Hordei Vulgaris Make and form, the mercury content in Semen Tritici aestivi is clearly required by country's limit standard, wherein limit Hg 0.02mg/Kg, according to " three Jin one jin of wine of grain " saying, Hg 0.06mg/Kg in Chinese liquor can be speculated.Therefore the Hg content in Chinese liquor will be well below this One standard.
As shown in Table 5, this experimental resin detect result is consistent with high-precision ICP testing result, and contrast adenine chelating Resin and 2-sulfydryl-1,3,4-thiadiazoles chelating resins can not check the mercury ion content in Chinese liquor complex system, the therefore present invention Chelating resin can effectively detect ion concentration of mercury in Chinese liquor.
In sum, the optimum synthesis condition of the novel chelate resin of the present invention is: N-methylthiourea and the-CH in chlorine ball2Cl's The ratio of the amount of material is 4:1, and reaction dissolvent is DMF, and synthesis reaction temperature is 90 DEG C, and reaction rotating speed is 300rmp, the chlorine of gained Ball function base conversion ratio is 97.0%；Optimal adsorption condition is: optimal adsorption pH value is 4.0, and the adsorption effect of gained is: 347 Mg/g, and can effectively detect the ion concentration of mercury in Chinese liquor.
Above-described embodiment limits the present invention, the technology that the mode of every employing equivalent or equivalent transformation obtains never in any form Scheme all falls within protection scope of the present invention.

Claims (5)

1. a preparation method for chelating resin, the method is with chlorine ball as parent, and N-methylthiourea is part, to the benzyl on chlorine ball Base is modified, and described chlorine ball is macroporous type chloroethyl crosslinked polystyrene microsphere；It is characterized in that described preparation method bag Include following steps:
1) chlorine ball is immersed in the DMF of reaction dissolvent, until chlorine ball is the most swelling；
2) in step 1) gains in add the N-methylthiourea as part and the sodium as catalyst, nitrogen protect Under conditions of protecting, at 85-95 DEG C, stirring is reacted 10-14 hour；Described N-methylthiourea and-CH in chlorine ball2The ratio of the amount of Cl material For 3-5:1；
3) filtration step 2) gains obtain filter cake；It is first colourless, then by filter cake reaction dissolvent washing by soaking to cleaning mixture With distilled water wash, more successively with dehydrated alcohol, acetone, ether and distilled water wash for several times, 45-55 DEG C of vacuum drying, obtain Chelating resin.
The preparation method of chelating resin the most according to claim 1, it is characterised in that:
Described step 1) in: chlorine ball with the amount ratio of N,N-dimethylformamide is: 1mg chlorine ball: the N of 0.5～1mL, N-bis- Methylformamide, soak time is 22～26 hours；
Described step 2) in, speed of agitator is 250-350r/min.
3. the application of the chelating resin that a preparation method as claimed in claim 1 or 2 prepares, it is characterised in that this application is mainly wrapped Include following steps:
1) in the chelating resin of preparation, add the NaAc_HAc buffer solution of pH=4.0, and soak 22-26h；
2) in step 1) gains in add mercury ion titer, in temperature 30-40 DEG C, the perseverance of rotating speed 140-160r/min Temperature agitator vibrates；Wherein chelating resin with the amount ratio of mercury ion standard solution is: 12-18mg chelating resin: 25ml hydrargyrum Ion standard solution；
3) chelating resin saturated adsorption capacity to cadmium ion is measured after balance upon adsorption.
4. the chelating resin that preparation method as claimed in claim 1 or 2 prepares is for a detection method for mercury ion, its feature It is that this detection method comprises the following steps:
(1) pre-treatment of testing sample: testing sample is preprocessed, micro-wave digestion, after cooling, obtain containing mercuric to be measured Solution；
(2) separation and preconcentration of chelating resin: solution to be measured regulation is placed on to pH=4.0 the dynamic adsorption post of chelating resin In, coutroi velocity is that 1.5-2.5mL/min passes through, and after dynamic adsorption terminates, adds strippant, with the stream of 0.5-1.5ml/min Speed carries out desorbing by described dynamic adsorption post, and detects outflow solution concentration.
Chelating resin the most according to claim 4 is for the detection method of mercury ion, it is characterised in that in described step (2) The HNO that strippant is 25-35mL 4mol/L3The mixed liquor of hydrochloric acid；Described testing sample is Chinese liquor.
CN201610068961.5A 2016-01-30 2016-01-30 Reparation and application of chelating resin and mercury ion detection method Pending CN105709703A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107602750A (en) * 2017-09-08 2018-01-19 中国神华能源股份有限公司 A kind of preparation method of deliming resin
CN107758717A (en) * 2017-09-08 2018-03-06 中国神华能源股份有限公司 A kind of method for liquor alumini chloridi deliming
CN111269340A (en) * 2020-03-31 2020-06-12 台州学院 Chelate resin with 1-methanesulfonyl piperazine as ligand and preparation method and application thereof
CN113318570A (en) * 2021-06-11 2021-08-31 浙江红狮环保股份有限公司 Method for removing mercury in flue gas
CN117563570A (en) * 2024-01-16 2024-02-20 西安金沃泰环保科技有限公司 Resin for protein adsorption and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1286274A (en) * 1999-08-27 2001-03-07 拜尔公司 Process for preparing monodisperse cross-linked bead polymer having thiourea group, and use thereof
CN104628906A (en) * 2015-02-05 2015-05-20 浙江工商大学 Preparation method of chelate resin capable of selectively adsorbing Hg (II)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1286274A (en) * 1999-08-27 2001-03-07 拜尔公司 Process for preparing monodisperse cross-linked bead polymer having thiourea group, and use thereof
CN104628906A (en) * 2015-02-05 2015-05-20 浙江工商大学 Preparation method of chelate resin capable of selectively adsorbing Hg (II)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈义镛: "聚乙烯苄硫脲大孔性螯合树脂的合成及其对金属离子螯合性的研究", 《高分子通讯》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107602750A (en) * 2017-09-08 2018-01-19 中国神华能源股份有限公司 A kind of preparation method of deliming resin
CN107758717A (en) * 2017-09-08 2018-03-06 中国神华能源股份有限公司 A kind of method for liquor alumini chloridi deliming
CN107758717B (en) * 2017-09-08 2020-03-13 中国神华能源股份有限公司 Method for removing calcium from aluminum chloride solution
CN111269340A (en) * 2020-03-31 2020-06-12 台州学院 Chelate resin with 1-methanesulfonyl piperazine as ligand and preparation method and application thereof
CN111269340B (en) * 2020-03-31 2020-12-29 台州学院 Chelate resin with 1-methanesulfonyl piperazine as ligand and preparation method and application thereof
CN113318570A (en) * 2021-06-11 2021-08-31 浙江红狮环保股份有限公司 Method for removing mercury in flue gas
CN113318570B (en) * 2021-06-11 2022-04-19 浙江红狮环保股份有限公司 Method for removing mercury in flue gas
CN117563570A (en) * 2024-01-16 2024-02-20 西安金沃泰环保科技有限公司 Resin for protein adsorption and preparation method thereof
CN117563570B (en) * 2024-01-16 2024-03-15 西安金沃泰环保科技有限公司 Resin for protein adsorption and preparation method thereof

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