CN109883885B - Evaluation method of uranium desorption effect of tea - Google Patents
Evaluation method of uranium desorption effect of tea Download PDFInfo
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Abstract
The invention discloses a method for evaluating uranium desorption effect of tea. According to the method, firstly, according to an alkali-acid-alkali preparation method, a bone glue solution is added in an acid stage of urea resin synthesis to prepare bone glue copolyurea resin, hydroxyapatite is added to prepare a urea resin-based bionic material, the urea resin-based bionic material is subjected to oscillation adsorption with uranium liquid to prepare the uranium-containing urea resin-based bionic material for simulating uranium-containing bones, and then the desorption effect of tea on uranium in the material is evaluated by changing the tea water soaking condition. The method determines that the green tea desorption effect is superior to that of oolong tea and black tea, the total desorption rate of the green tea to uranium five-time desorption is more than 85%, the dense tea desorption effect is superior to that of light tea, and the overnight tea desorption effect is superior to that of newly brewed tea. The evaluation method can be used for distinguishing the desorption effects of different types of tea and reducing the internal irradiation hazard of uranium to human bodies by determining the optimal tea drinking mode. The method can be used as reference material for discharging uranium in tea drinking of radiation workers.
Description
Technical Field
The invention belongs to the technical field of bionic materials, and particularly relates to a method for evaluating uranium desorption effect of tea.
Background
Internal irradiation hazards caused by uranium pollution in water bodies are always a major concern of people. The main reason for the hazard of internal irradiation is the bonding of uranium to bone. Uranium is mainly UO in water2 2+The form exists that when people drink uranium-bearing water by mistake, the UO2 2+Absorbed by intestinal tract, enters blood, and is transferred to liver, kidney, bone and other organs. Uranium has chemical toxicity and radioactivityThe toxic side effects are mainly chemical toxicity to liver and kidney, and radiation-induced damage to bone. Internal irradiation is more harmful than chemical toxicity because uranium can attach to the bone surface for a long period of time and the resulting internal irradiation can induce cellular carcinogenesis.
The bone comprises bone tissue, periosteum and bone marrow, and the bone tissue consists of collagen fiber and hydroxyapatite; the periosteum is arranged outside the bone tissue, and nerves, tissues and blood vessels are distributed on the periosteum; the bone marrow is inside the bone tissue. The uranium is bound to the bone by contacting the blood vessels, the UO in the blood vessels, with the bone tissue2 2+With HCO3 -Generates uranyl carbonate ions, the uranyl carbonate ions penetrate through the vessel wall to exchange with bone tissues, and a large amount of uranium is enriched on bones. At present, animal experiments, mathematical models and other methods are mostly adopted to research the uranium and bone combination condition, the animal experiment result is more accurate, but the period is long, the uncontrollable factors are more, the subsequent treatment is troublesome (Aiguping, and the like, pathological morphological characteristics of rats after long-term intake of depleted uranium are observed [ J]Liberation of the journal of military medicine, 2007,32(10): 1036-. The mathematical model does not require experimentation, but is computationally expensive and requires formula and parametric support (Lishijun. estimation of internal dose of inhaled uranium compounds [ J]Radiation protection, 1985, (1): 24-33). Bones cannot be used as in vitro research objects due to their complex structure and easy degeneration.
In order to reduce the irradiation harm of uranium to human bodies, drug excretion promotion is mostly adopted, but the side effect of drugs to human bodies is not clear, so that a more appropriate uranium excretion promoter needs to be searched. The main component of tea water is tea polyphenol, and the combination of polyphenol substances and metal ions is reported (M Gurung, et al, additive removal of Cs (I) from aqueous solution using polyphenols engineered biological-based adsorbents [ J ] Chemical Engineering Journal,2013,231(17):113-120), so that the tea water can be used as a desorbent or discharge promoter of uranium.
Disclosure of Invention
The invention aims to provide a method for evaluating uranium desorption effect of tea.
The technical solution for realizing the purpose of the invention is as follows:
the evaluation method of the uranium desorption effect by tea comprises the following steps of oscillating and adsorbing a urea-formaldehyde resin-based bionic material and uranium liquid to prepare a uranium-containing urea-formaldehyde resin-based bionic material and simulate a uranium-containing bone, and determining the best tea drinking mode to reduce the internal irradiation harm of uranium to a human body by changing the tea water soaking condition and combining the desorption effect of the tea on the uranium in the material, wherein the method comprises the following specific steps:
3, under the constant-temperature oscillation condition of 37 ℃, putting the uranium-containing urea-formaldehyde resin-based bionic material into tea water with the pH value of 7.0-7.5 for desorption, wherein the desorption time is 1-48 h, and measuring the uranium concentration of the reacted tea water according to a formula QDesorption ofCalculating the desorption quantity Q of the tea to the uranium in the uranium-containing urea-formaldehyde resin-based bionic materialDesorption ofWherein Q isDesorption ofThe uranium desorption amount is mg/g of the tea water; c is the uranium concentration of the tea water after the reaction time t, mg/L; v is the volume of tea water, L; and m is the mass of the uranium-containing urea-formaldehyde resin-based bionic material, and g.
Preferably, in the step 1, the mass of the bone glue is 10-50% of the mass of the urea-formaldehyde resin.
Preferably, in the step 1, the adding amount of the hydroxyapatite is determined according to the ratio of the collagen fiber to the hydroxyapatite in the bone tissue, and is 60-90% of the mass of the bone glue.
Preferably, in the step 2, the mass ratio of the urea-formaldehyde resin-based bionic material to the uranium liquid is 0.1-10: 100.
Preferably, in the step 3, the tea leaves in the tea water are soaked in water at a temperature of 100 ℃ for 1-48 h at a mass ratio of 1-4: 100.
Preferably, in the step 3, the mass ratio of the uranium-containing urea-formaldehyde resin-based bionic material to the tea water is 1-5: 10.
Compared with the existing animal experiment and mathematical model methods, the method has the advantages that:
(1) the desorption process of the tea water to the uranium in the bone can be simulated in vitro, the experimental period is short, the uncontrollable factors are few, the operation is simple, and the calculation is convenient.
(2) The urea-formaldehyde resin-based bionic material adopted by the method can combine bone tissue components together, the bone tissue components mainly comprise collagen fibers and hydroxyapatite, the bone glue and the collagen fibers have the same components, but the bone glue is easy to dissolve in water and cannot be directly mixed with the hydroxyapatite, amino and amide groups contained in the urea-formaldehyde resin can be combined with the bone glue, meanwhile, the hydroxyapatite can be bonded in the material by the viscosity of the resin, the urea-formaldehyde resin-based bionic material has simple composition and the performance similar to that of uranium adsorption of bones, the simulated uranium-containing bones can be prepared through the adsorption process and used for desorption research of experiments, the urea-formaldehyde resin is a material synthetic matrix, the water-insoluble characteristic of the urea-formaldehyde resin-based bionic material is similar to that of proteins, the urea-formaldehyde resin-based material can be regarded as soft tissues around the bone tissues, and the experimental results cannot be interfered.
(3) The tea polyphenols in the tea water can be mixed with UO2 2+Therefore, the tea water has desorption effect on uranium, different tea types have different desorption effect, and related desorption results can be used as reference data for discharging uranium when radiation workers drink tea.
Drawings
Fig. 1 is a graph showing the change of the uranium adsorption amount of the urea-formaldehyde resin-based biomimetic material in example 2 with the reaction time.
Fig. 2 is a graph showing the desorption effect of different tea water on uranium in the uranium-containing urea-formaldehyde resin-based biomimetic material in embodiment 3.
Fig. 3 is a graph showing the influence of the pH value on the desorption of uranium in the uranium-bearing urea-formaldehyde resin-based biomimetic material from tea in example 4.
Figure 4 is a graph of the effect of green tea concentration and tea infusion time on uranium in the desorbent material in example 5.
FIG. 5 is a graph showing the total desorption rate of green tea in example 6 as a function of the cumulative desorption times.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawings.
Example 1
The preparation method of the urea-formaldehyde resin-based bionic material comprises the following specific steps:
And 2, adding bone glue solution in the acid stage of urea resin synthesis according to the alkali-acid-alkali preparation method to prepare the bone glue copolymerized urea resin.
And 3, drying the bone glue copolymerized urea-formaldehyde resin at 70 ℃ to be viscous, adding hydroxyapatite, uniformly stirring, drying at 70 ℃, crushing and sieving to prepare the urea-formaldehyde resin based bionic material, wherein the adding amount of the hydroxyapatite is determined according to the ratio of collagen fibers to the hydroxyapatite in bone tissues and is 70% of the mass of the bone glue.
Example 2
The preparation method of the uranium-containing urea-formaldehyde resin-based bionic material comprises the following specific steps:
And 2, washing the obtained filter residue with deionized water, drying at 70 ℃, crushing and sieving to obtain the uranium-containing urea-formaldehyde resin-based bionic material.
The uranium content in the uranium-containing urea-formaldehyde resin-based bionic material after 12h of reaction is calculated to be 73.41mg/g by measuring the uranium liquid concentration before and after the reaction, the material is used as a material for a subsequent desorption experiment, the change condition of the uranium adsorption capacity of the material along with the reaction time is shown in figure 1, and the uranium adsorption capacity reaches the balance after 12h of adsorption as can be seen from figure 1.
Example 3
Desorbing uranium in the uranium-containing urea-formaldehyde resin-based bionic material by using different types of tea, and carrying out desorption in a constant-temperature oscillation box. The tea is selected from black tea (Jinjunmei), oolong tea (Tieguanyin) and green tea (Biluochun), the soaking mass ratio of the tea to water is 1:50, the soaking temperature is 100 ℃, and the soaking time is 1 h. The pH of black tea is 5.0, oolong tea is 5.4, green tea is 6.0 by pH meter, and considering that the pH value of human tissue fluid is 7.0-7.5, the pH of tea water is adjusted to 7.0 by hydrochloric acid and sodium hydroxide. 10g of the uranium-containing urea-formaldehyde resin-based bionic material is placed in 100mL of different tea water for desorption, the desorption temperature is 37 ℃, the desorption time is 0.5-48 h, and the uranium desorption amount of the tea is measured, and the result is shown in figure 2. As can be seen from FIG. 2, after 24 hours of desorption, the balance is achieved, the uranium desorption amount of black tea is 21.41mg/g, the uranium desorption amount of oolong tea is 23.94mg/g, the uranium desorption amount of green tea is 26.45mg/g, and the uranium desorption amount of water is 6.46mg/g, so that the tea water desorption effect is better than that of water, and the green tea desorption effect is the best among the three teas because the green tea has the highest tea polyphenol content and can react with more UO2 2+Binding facilitates desorption.
Example 4
Desorbing uranium in the uranium-containing urea-formaldehyde resin-based bionic material by using tea water with different pH values, and carrying out desorption in a constant-temperature oscillation box. The tea is selected from black tea (Jinjunmei), oolong tea (Tieguanyin) and green tea (Biluochun), the soaking mass ratio of the tea to water is 1:50, the soaking temperature is 100 ℃, and the soaking time is 1 h. Since the pH value of the tissue fluid at different parts of the human body has a certain difference, and the approximate change range is 6.0-9.0, the pH value of the tea water is adjusted to 6.0-8.0 by using hydrochloric acid and sodium hydroxide. 10g of the uranium-containing urea-formaldehyde resin-based biomimetic material is put into 100mL of tea water with different pH values for desorption, the desorption temperature is 37 ℃, the desorption time is 24h, and the uranium desorption amount of the tea is measured, and the result is shown in figure 3. As can be seen from FIG. 3, the amount of uranium desorbed from tea increases with increasing pH, because OH is more basic-Is easier to be combined with UO2 2+Binding promotes desorption. Green tea at different pH valuesThe desorption effect on uranium is best.
Example 5
Desorbing uranium in the uranium-containing urea-formaldehyde resin-based bionic material by using green tea with different concentrations and different soaking times, and carrying out desorption in a constant-temperature oscillation box. Soaking the tea leaves in water at a soaking temperature of 100 ℃ for 1-48 h at a soaking mass ratio of 1-4: 100, and adjusting the pH of the green tea to 7.0 by using hydrochloric acid and sodium hydroxide. 10g of the uranium-containing urea-formaldehyde resin-based bionic material is put into 100mL of green tea for desorption, the desorption temperature is 37 ℃, the desorption time is 24h, and the uranium desorption amount of the tea is measured, and the result is shown in figure 4. As can be seen from FIG. 4, the desorption effect of the concentrated tea is significantly better than that of the light tea, and the desorption effect of the overnight tea (longer soaking time) is better than that of the freshly brewed tea. When the tea leaves and water are soaked in water at a mass ratio of 1:25 for 48 hours, the uranium desorption amount of the green tea can reach 32.61 mg/g.
Example 6
Desorbing uranium in the uranium-containing urea-formaldehyde resin-based bionic material for multiple times by using green tea, and desorbing in a constant-temperature oscillation box. The desorption process of uranium by drinking tea for multiple times of human bodies is simulated through the desorption times. The soaking mass ratio of the tea leaves to the water is 1:25, the soaking temperature is 100 ℃, the tea leaves are soaked for 1h, and the pH value of the green tea is adjusted to 7.0 by hydrochloric acid and sodium hydroxide. 10g of the uranium-containing urea-formaldehyde resin-based bionic material is placed in 100mL of green tea for desorption, continuous desorption is carried out for 5 times, the desorption temperature is 37 ℃, the desorption time is 24 hours, and the uranium desorption amount of the tea is determined, the result is shown in figure 5, the total desorption rate in figure 5 is the percentage of the total uranium desorption amount in the uranium content, and the total uranium desorption amount is the accumulated value of the n-th uranium desorption amount corresponding to the n-th tea desorption (n is more than or equal to 1). As can be seen from figure 5, the total desorption rate of 5 times of desorption of green tea can reach more than 85%, which indicates that the tea drinking for many times has good uranium discharge effect.
Claims (4)
1. The method for evaluating the uranium desorption effect of tea is characterized by comprising the following specific steps:
step 1, according to an alkali-acid-alkali preparation method, adding bone glue solution at an acidic stage of urea resin synthesis to prepare bone glue copolymerized urea resin, drying the bone glue copolymerized urea resin to be viscous, adding hydroxyapatite, uniformly stirring, drying, crushing and sieving to prepare a urea resin-based bionic material, wherein the mass of the bone glue is 10-50% of that of the urea resin, and the adding amount of the hydroxyapatite is determined according to the ratio of collagen fibers to the hydroxyapatite in bone tissues and is 60-90% of that of the bone glue;
step 2, placing the urea-formaldehyde resin-based bionic material in uranium liquid for adsorption for 0.5-12 h under the constant-temperature oscillation condition of 37 ℃ to obtain the uranium-containing urea-formaldehyde resin-based bionic material, and measuring the concentration of the uranium liquid before and after reaction according to a formula QAdsorption＝(C0-Ce) X V/m, calculating the uranium content Q of the uranium-containing urea-formaldehyde resin-based bionic materialAdsorptionWherein Q isAdsorptionThe content of uranium in the uranium-containing urea-formaldehyde resin-based bionic material is mg/g; c0The initial concentration of uranium liquid is mg/L; ceThe uranium liquid concentration after the reaction time t is mg/L; v is the volume of uranium liquid, L; m is the mass of the urea-formaldehyde resin-based bionic material, g;
3, under the constant-temperature oscillation condition of 37 ℃, putting the uranium-containing urea-formaldehyde resin-based bionic material into tea water with the pH value of 7.0-7.5 for desorption, wherein the desorption time is 1-48 h, and measuring the uranium concentration of the reacted tea water according to a formula QDesorption ofCalculating the desorption quantity Q of the tea to the uranium in the uranium-containing urea-formaldehyde resin-based bionic materialDesorption ofWherein Q isDesorption ofThe uranium desorption amount is mg/g of the tea water; c is the uranium concentration of the tea water after the reaction time t, mg/L; v is the volume of tea water, L; and m is the mass of the uranium-containing urea-formaldehyde resin-based bionic material, and g.
2. The evaluation method according to claim 1, wherein in the step 2, the mass ratio of the urea-formaldehyde resin-based bionic material to the uranium liquid is 0.1-10: 100.
3. The evaluation method according to claim 1, wherein in the step 3, the tea leaves and water are soaked at a temperature of 100 ℃ for 1-48 h at a mass ratio of 1-4: 100.
4. The evaluation method according to claim 1, wherein in the step 3, the mass ratio of the uranium-containing urea-formaldehyde resin-based bionic material to the tea water is 1-5: 10.
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