CN113851244A - Method for treating wastewater containing radioactive isotope carbon-14 - Google Patents
Method for treating wastewater containing radioactive isotope carbon-14 Download PDFInfo
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The application aims to provide a method for treating carbon-14-containing wastewater generated in the research process of radioactive isotope carbon-14 labeling synthesis and tracing. The method can effectively solve the problem that the carbon-14-containing wastewater in the current radiochemical laboratory in China can only be temporarily stored and accumulated and can not be treated, so that the carbon-14-containing wastewater can not be solidified, transported and finally treated according to the method.
Description
Technical Field
The invention belongs to the field of radioactive waste treatment, and particularly relates to a carbon-14 labeled synthetic process of a radioactive isotope of a chemical and a treatment method for generating carbon-14-containing wastewater in tracing research of the carbon-14 labeled chemical in a complex system.
Background
Carbon-14 is a radioactive isotope of carbon with a half-life of 5730 years, releasing low-energy soft beta rays upon decay. The carbon-14 marker is one of commonly used tracers for researching the movement change rule (absorption, running, distribution, metabolism, mass balance and the like) of corresponding compounds in a complex system (including human bodies, animals, plants, microorganisms, soil-water, cells and the like), and has the advantages of intuition, sensitivity, strong specificity, no interference of environmental matrixes and the like. Although standards and research methods in the fields of medicine, pesticides, veterinary medicine, environment and the like do not clearly specify that a carbon-14 marker must be adopted, in fact, many necessary and critical test data and information cannot be provided only by means of traditional non-radioactive substances, and can be obtained only by means of the carbon-14 marker in such cases [ national drug administration, pharmaceutical non-clinical research quality management regulations [ S ]. 2017-07-27; the quality control standard of the drug clinical trial [ S ] 2020-04-26; ministry of agriculture, veterinary clinical trial quality management Specification [ S ].2015-12-09 ]. For example, in the area of innovative Drug Development, pharmacokinetic studies of more than 80% of the innovative drugs internationally (including preclinical animal trials and clinical human trials) were conducted using carbon-14 labeled drugs, which are the gold standard for basic studies of internationally recognized Drug tissue distribution, metabolite structure identification, mass balance [ Lappin G, simple s.radiotracers in Drug Development [ M ]. Florida: CRC Press, Taylor & Francis Group, 2006; weimingji, Zhaoming, Innovative drug pharmacokinetics research and evaluation [ M ]. Beijing, Beijing university medical Press, 2008: 354; clock amplification, Li birch, drug metabolism in drug design and development-basic principle and practice [ M ]. Beijing, civil military medical Press, 2011 ]; internationally, the research on metabolism in crops, metabolism in soil-water and metabolism in livestock and poultry must be carried out by using carbon-14 labeled pesticides in pesticide registration metabolism tests so as to accurately evaluate the safety of the pesticides on agricultural products and natural environment [ Ministry of agriculture, pesticide metabolism test criteria NY/T3096-2017 [ S ].2017-06-12 in crops; pesticide metabolism test criterion NY/T3557 and 2020[ S ] 2020-03-20 in livestock and poultry in agricultural rural areas; in the field of environmental science, researches on metabolic mechanism, degradation process and environment return of a plurality of organic chemicals in media such as soil, water and the like must be carried out by means of a carbon-14 marker [ economic cooperation and development histochemical test criterion compiling committee, economic cooperation and development histochemical test criterion [ M ]. Beijing: Chinese agriculture press, 2013:1367 ]; in the field of medical diagnosis, carbon-14 labeled urea prepared from carbon-14 labeled barium carbonate has long been commercially available on a large scale for the detection of helicobacter pylori in humans.
The preparation of the carbon-14 label usually involves various radiosynthesis reactions to obtain a crude product, which is often subjected to purification by reverse phase preparative high performance liquid chromatography to obtain the final carbon-14 label. A few radiosynthesis reactions use water as the reaction medium; most post-treatment reactions of radiosynthesis require water; pure water is the main component of the mobile phase in the reversed-phase preparative high performance liquid chromatography [ novel herbicide propyl ester oxalether A ring14C-average marker Synthesis and identification [ J]Journal of chemistry, 2005,63(21): 1999; synthesis of 6 beta- ([1-14C]propoxy)celangulin V.J Label Compd Radiopharm,2008,51(2):109；Synthesis of herbicidal ZJ0273 labeled with tritium and carbon-14[J].J Label Compd Radiopharm,2008,51(4):182；Synthesis of carbon-14 labeled ZJ0712,a novel strobilurin fungicide[J]J Label company Radiopharm,2018,61(11): 812; synthesis and analysis of two radioisotopes, carbon-14 labeled Dufulin [ J]Organic chemistry, 2018,38(5):1177]. Carbon-14-containing wastewater is inevitably produced in all of these processes. Similarly, the processes of culturing, extracting, purifying and analyzing biogenic materials in tracer studies (innovative drug pharmacokinetics, pesticide registration metabolism, etc.) using carbon-14 markers must inevitably produce carbon-14-containing wastewater [ Determination of biological ZJ0273 residue in cultured by radioactive microbiological tracing method. food Chem,2009,114(1):300]. The cleaning process using glass or the like in the test also necessarily produces carbon-14-containing waste water. The radionuclide concentration or specific activity in the carbon-14 containing wastewater produced during the above test is often much greater than the nationally determined level of cleanliness control. The carbon-14-containing waste water belongs to high-risk waste strictly controlled by national laws and regulations, and extremely strict requirements are placed on the final treatment of the waste water [ environmental protection department, etc.. classification of radioactive waste [ S ]].2017-12-01]. Therefore, the carbon-14-containing wastewater must be pretreated under the principles of consistent minimization, harmlessness, proper disposal and permanent safety, so that the treated carbon-14-containing wastewater is finally solidified, transported, stored and finally safe by a qualified unit according to the regulations of the safety management of radioactive wastes (State Council, 2011-12-20)And (4) disposing to realize the final safe disposal of the radioactive waste.
In recent years, the demand of the research and development fields of domestic medicines, pesticides, veterinary medicines, environment and the like on the carbon-14 marker is continuously increased, and the synthesis research of the domestic carbon-14 marker is gradually started; although the total activity of carbon-14 required for carbon-14 tracing is much less compared to label synthesis, the number of enterprises based on carbon-14 tracing studies is rapidly increasing. Thus, the domestic demand for carbon-14 markers is rapidly increasing, and the amount of carbon-14-containing wastewater generated is increasing. The half-life period of the carbon-14 is long, and the potential hazard of the carbon-14-containing wastewater to the natural environment is extremely high; in addition, the price of the carbon-14 is very expensive, which makes the volume reduction and carbon-14 recycling of the wastewater necessary and urgent. It should be noted that carbon-14 has long been a scarce resource internationally, and its production and preparation technology is high, its investment threshold is high, and its maintenance cost is large; methods and techniques related to the synthesis of carbon-14 markers, including the treatment of carbon-14-containing waste, are monopolized abroad [ national atomic energy agency et al. medical isotope medium-long term development program (2021 + 2035.). 2021-06-24 ].
Currently, there are many reports on methods for treating wastewater containing radioactive isotopes in China, but these reports are all the treatments for generating a large amount of wastewater in the field of nuclear power and nuclear power, nuclear weapons and other power nuclear technologies [ radioactive wastewater source and treatment method overview and evaluation [ J ]. sichuan environment, 2019,38(02): 108; the development of the medium-low level radioactive wastewater treatment technology: the seventeenth national nuclear electronics and nuclear detection technology academic annual meeting [ C ], lang, gansu, china, 2014; research progress of low-radioactivity wastewater treatment technology [ J ]. Hebei chemical industry, 2013,36(3): 64; radioactive waste water treatment technology [ J ] Guangdong chemical industry, 2013,40(13): 133; research progress of radioactive wastewater concentration treatment technology: the first China Command control conference [ C ], Beijing, China, 2013; the radioactive wastewater treatment method and domestic and foreign treatment conditions are as follows: the academic annual meeting collection of the society of environmental science of China [ C ], Wuhan Hubei, 2009, China. The waste water contains a plurality of radioactive metal elements and non-metal elements, the half-life periods of the waste water are different, and a plurality of rays including high-energy gamma rays with extremely strong penetrating power are released at the same time, so that the danger is extremely high; the radioactive isotopes contained in these nuclear industrial wastewater exist mainly in the state of inorganic substances having various chemical forms, and thus the treatment thereof is extremely difficult. The research on the synthesis and tracing application of carbon-14 label belongs to the technical field of civil non-power nucleus, the radioactivity of the waste water generated in the process only comes from carbon-14 which releases soft beta rays, and the carbon-14 exists in organic compounds with various chemical forms.
So far, no unit with carbon-14-containing wastewater treatment qualification is identified by the ecological environment department in China, and no report of carbon-14-containing wastewater treatment is seen in the literature. In practice, the radioactive waste stored and disposed of in the national radioactive waste reservoir after storage is all in solid state; problems such as leakage, volatilization and the like of radioactive carbon-14-containing waste liquid can occur during long-term storage and disposal of the waste liquid in a national radioactive waste storage due to the fact that the radioactive carbon-14-containing waste liquid is difficult to seal and solidify, and the national radioactive waste storage cannot store the carbon-14-containing waste liquid all the time [ ecological environment department, radioactive waste treatment, storage and disposal permission management method (petition comments). 2018-07-30 ]. Therefore, domestic chemical laboratories have to collect and temporarily store carbon-14-containing wastewater generated for many years according to the requirements of regulations and have to store the wastewater for a long time. With the accumulation of such carbon-14 containing wastewater for many years, the possibility of leakage, volatilization and the like of these high-risk radioactive wastewater increases, which poses a potential threat to the temporary storage, public safety and natural environmental safety. This not only results in a significant increase in the difficulty and cost of the post-stage classification treatment of the radioactive wastewater, but also restricts the sustainable, healthy and high-quality development of carbon-14 labeled synthesis and tracing techniques and methods systems that have urgent application requirements in medicine, pesticides, veterinary drugs, etc.
Therefore, there is a need in the industry for a solution that substantially solves the above problems. In view of the above, the patent provides a practical, efficient and economical method for treating carbon-14-containing wastewater, which is easy to popularize, and the method is not only suitable for pretreatment of the carbon-14-containing wastewater after storage in a national radioactive waste storage and before storage and disposal, but also can enrich and recover the carbon-14. Therefore, the invention should be developed.
Disclosure of Invention
In view of the above, the present application is directed to a method for treating carbon-14-containing wastewater generated during the synthesis and tracer studies of radioisotope labeled with carbon-14. The method can effectively solve the problem that the carbon-14-containing wastewater in the current radiochemical laboratory of China can only be temporarily stored and accumulated and can not be treated, so that the carbon-14-containing wastewater can not be solidified, transported and finally treated according to the method, and the treatment method comprises the following steps:
the method comprises the following steps: oxidizing organic matters in the wastewater containing the radioisotope carbon-14, then precipitating partial organic matters containing the radioisotope carbon-14 by using a flocculating agent, and filtering to obtain a filter cake A and a filtrate I; the amount of the flocculant used is not particularly limited so long as the flocculant can be flocculated as a whole, and is not limited to a certain amount, and the amount of the flocculant used is not limited to a certain amount, and is different depending on factors such as the concentration of wastewater containing radioactive isotopes.
Step two: adding inorganic strong base into the filtrate I for high-temperature alkaline hydrolysis, and distilling to obtain distillation residue B and distillate II;
step three: adding activated carbon into the distillate II, stirring and heating to slightly boil, preserving heat and filtering, and recovering residual activated carbon C to obtain a water phase III;
step four: adding macroporous adsorption resin into the water phase III, stirring uniformly at room temperature, standing, filtering and recovering residual adsorption resin D to obtain a water phase IV, and detecting the concentration of the radionuclide;
step five: and if the concentration of the radionuclide in the water phase IV exceeds the cleaning solution level, repeating the third step and the fourth step, or combining or recycling the first step to the fourth step until the concentration of the radionuclide in the water phase IV is less than the cleaning solution level.
The invention has the beneficial effects that:
the invention is practical and efficient for treating the carbon-14-containing wastewater, simultaneously realizes the recovery of the carbon-14, has safe operation process to the natural environment, low operation cost and easy popularization, and provides an effective and low-cost pretreatment method for the final legal disposal of the carbon-14-containing wastewater.
In a preferred embodiment of this embodiment, ozone or chlorine is used in the organic oxidation in the first step, and the stirring is performed when ozone or chlorine is introduced fully or in excess.
As a preferred embodiment of this embodiment, the inorganic strong base in step two includes potassium hydroxide and sodium hydroxide, and the temperature of the high-temperature alkaline hydrolysis is 70 to 110 ℃ for 0.5 to 2 hours.
As a preferred embodiment of this embodiment, in the third step, the addition amount of the activated carbon is 10 to 30g/L, the mixture is stirred in a slightly boiling state until the activity concentration of carbon-14 in the liquid phase does not decrease, and the mixture is allowed to stand and cool, so as to separate a solid-liquid two phase; and (4) temporarily storing the residual activated carbon C for later use, and carrying out next treatment on the obtained water phase III.
As a preferred embodiment of this embodiment, in the fourth step, the addition amount of the macroporous adsorption resin is 30 to 60g/L, standing at room temperature until the activity concentration of carbon-14 in the liquid phase does not decrease, and separating the solid-liquid two phases; and temporarily storing the treated residual adsorption resin for later use, and collecting and temporarily storing the residual adsorption resin according to the concentration of the obtained water phase IV radionuclide or carrying out the next treatment.
Drawings
FIG. 1 is a process scheme of the present invention.
Figure 2 is a block diagram of the carbon-14 labeled drug clevidipine for treating hypertension.
FIG. 3 is a block diagram of the carbon-14 labeled cabazitaxel drug for the treatment of prostate cancer.
FIG. 4 is a structural diagram of a medicament arformoterol marked by carbon-14 for treating chronic obstructive pulmonary disease.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be noted that, the steps one, two, three and four are only for naming each step, and there is no precedence order, and any combination or single use of a single step may be used in actual operation.
Note that, in fig. 2, 3, and 4, the marked position of "") is a carbon-14 position.
Example 1:
clevidipine (Clevidipine) is a dihydropyridine calcium channel blocker for ultra-short-acting intravenous injection and is mainly used for treating hypertension. Slave [ 2 ]14C]The technical route for preparing the carbon-14 marker of clevidipine by barium carbonate is shown in figure 2 (the asterisk marks the carbon-14 marking site, the same below). The treatment method of the carbon-14-containing wastewater generated in the process comprises the following steps:
the first step is as follows: introducing ozone or chlorine into carbon-14-containing wastewater (1L, 3.28E +7Bq/L) at room temperature under stirring for about 30min, and standing for 3 h; then adding a flocculating agent into the waste liquid to precipitate polymeric ferric chloride or polymeric aluminum chloride (3g), and stirring for 30 min; standing overnight, and filtering to obtain a filter cake A (0.22E +7Bq) and a filtrate I (3.06E +7 Bq/L);
a second part: adding inorganic strong base potassium hydroxide or sodium hydroxide (5g) into the filtrate I, heating to 70-90 ℃, stirring for 30min, and distilling to obtain distillation residue B (1.98E +7Bq) and distillate II (1.08E +7 Bq/L);
the third step: adding activated carbon (10g) into the distillate II, stirring and heating to slightly boil, keeping the temperature for min, filtering, and recovering residual activated carbon (6.41E +6Bq) to obtain a water phase III (4.40E +6 Bq/L);
the fourth step: adding HJ-07 macroporous adsorbent resin (30g) into the water phase III, stirring uniformly at room temperature, standing, and filtering to recover residual adsorbent resin (4.40E +6Bq) to obtain a water phase IV (8.26E +4 Bq/L);
the fifth step: adding D101 macroporous adsorbent resin (30g) into the water phase IV, stirring uniformly at room temperature, standing, and filtering to recover residual adsorbent resin (8.25E +4Bq) to obtain water phase IV (1.12E +2 Bq/L).
The solution-state radioactive substance (3.28E +7Bq) is converted into a solid state (the solid state radioactive substance can be recycled at the later stage) by the method, and the conversion rate is 99.99%.
Example 2:
cabazitaxel (Cabazitaxel) belongs to taxane anti-drugsA tumor medicine is mainly used for treating hormone refractory metastatic prostate cancer. Slave [ 2 ]14C]The technical route for preparing cabazitaxel carbon-14 marker by barium carbonate is shown in figure 3 (asterisk marks carbon-14 marker site). The treatment method of the carbon-14-containing wastewater generated in the process comprises the following steps:
the first step is as follows: introducing ozone or chlorine into the carbon-14-containing wastewater (1L, 4.10E +7Bq/L) at room temperature for about 30min under stirring, and continuing stirring for 3 h; then adding a flocculating agent into the waste liquid to precipitate polymeric ferric chloride or polymeric aluminum chloride (3g), and stirring for 30 min; standing overnight, and filtering to obtain a filter cake A (0.36E +7Bq) and a filtrate I (3.74E +7 Bq/L);
a second part: adding inorganic strong base potassium hydroxide or sodium hydroxide (8g) into the filtrate I, heating to slightly boil (90-110 ℃), continuing stirring for 2h, and distilling to obtain distillation residue B (3.53E +7Bq) and distillate II (2.08E +6 Bq/L);
the third step: adding activated carbon (30g) into the distillate II, stirring and heating to slightly boil, keeping the temperature for min, filtering, and recovering residual activated carbon (1.68E +6Bq) to obtain a water phase III (4.12E +5 Bq/L);
the fourth step: adding ADS-7 macroporous adsorbent resin (30g) into the water phase III, stirring at room temperature, standing, filtering, and recovering residual adsorbent resin (3.33E +5Bq) to obtain water phase IV (7.91E +4 Bq/L);
the fifth step: adding CAD-40 macroporous adsorption resin (30g) into the water phase IV, stirring uniformly at room temperature, standing, and then filtering to recover residual adsorption resin (7.86E +4Bq) to obtain the water phase IV (5.36E +2 Bq/L).
The solution-state radioactive substance (4.10E +7Bq/L) is converted into a solid state (the solid state radioactive substance can be recycled at the later stage) by the method, and the conversion rate is 99.99%.
Example 3:
arformoterol (Arformoterol) is a long-acting beta2-adrenoceptor agonists, for clinical use in the treatment of chronic obstructive pulmonary disease. Slave [ 2 ]14C]The technical route for preparing cabazitaxel carbon-14 marker by barium carbonate is shown in figure 3 (asterisk marks carbon-14 marker site). The treatment method of the carbon-14-containing wastewater generated in the process comprises the following steps:
the first step is as follows: adding flocculant to carbon-14-containing wastewater (1L, 1.25E +7Bq/L) under stirring at room temperature to precipitate polymeric ferric chloride or polymeric aluminum chloride (3g), and stirring for 30 min; standing overnight, and filtering to obtain a filter cake A (0.19E +7Bq) and a filtrate I (1.06E +7 Bq/L);
a second part: adding activated carbon (10g) into the filtrate I, heating to slightly boil, continuing stirring for 30min, filtering, and recovering residual activated carbon (7.96E +5Bq) to obtain filtrate II (2.64E +5 Bq/L);
the third step: adding AB-8 macroporous adsorbent resin (20g) into the filtrate II, stirring at room temperature, standing overnight, and filtering to recover residual adsorbent resin (2.08E +5Bq) to obtain water phase IV (5.62E +4 Bq/L);
a fourth step of: adding activated carbon (20g) into the filtrate I, heating to slightly boil, continuing stirring for 30min, filtering, and recovering residual activated carbon (5.58E +4Bq) to obtain filtrate II (4.08E +2 Bq/L);
the solution-state radioactive substance (1.25E +7Bq/L) is converted into a solid state (the solid state radioactive substance can be recycled at the later stage) by the method, and the conversion rate is 99.99%.
Many modifications may be made by one of ordinary skill in the art in light of the above teachings. Therefore, it is intended that the invention not be limited to the particular details of the embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (6)
1. A method for treating wastewater containing radioactive isotope carbon-14, comprising:
the method comprises the following steps: oxidizing organic matters in the wastewater containing the radioisotope carbon-14, then precipitating partial organic matters containing the radioisotope carbon-14 by using a flocculating agent, and filtering to obtain a filter cake A and a filtrate I;
step two: adding inorganic strong base into the filtrate I for high-temperature alkaline hydrolysis, and distilling to obtain distillation residue B and distillate II;
step three: adding activated carbon into the distillate II, stirring and heating to slightly boil, preserving heat and filtering, and recovering residual activated carbon C to obtain a water phase III;
step four: adding macroporous adsorption resin into the water phase III, stirring uniformly at room temperature, standing, filtering and recovering residual adsorption resin D to obtain a water phase IV, and detecting the concentration of the radionuclide;
step five: if the radionuclide concentration of the water phase IV exceeds the cleaning solution level, repeating the third step and the fourth step until the radionuclide concentration is less than the cleaning solution level.
2. The process of claim 1, comprising: in the first step, ozone or chlorine is adopted for organic oxidation, and stirring is carried out when the ozone or chlorine is fully or excessively introduced.
3. The process of claim 1, comprising: and the inorganic strong base in the second step comprises potassium hydroxide and sodium hydroxide, the high-temperature alkaline hydrolysis temperature is 70-110 ℃, and the time is 0.5-2 h.
4. The process of claim 1, comprising: in the third step, the addition amount of the activated carbon is 10-30 g/L, the mixture is stirred in a micro-boiling state until the activity concentration of carbon-14 in the liquid phase is not reduced, and the mixture is kept stand and cooled to separate a solid phase and a liquid phase; the residual activated carbon C is temporarily stored for later use, and the obtained water phase III is subjected to next treatment.
5. The process of claim 1, comprising: in the fourth step, the addition amount of the macroporous adsorption resin is 30-60 g/L, standing at room temperature until the activity concentration of carbon-14 in the liquid phase does not decrease any more, and separating a solid-liquid two phase; and temporarily storing the treated residual adsorption resin for later use, and collecting and temporarily storing the residual adsorption resin according to the concentration of the radionuclide in the obtained water phase IV or carrying out the next treatment.
6. The process of claim 1, comprising: and (3) according to different chemical structures of the carbon-14-containing components in the waste liquid, combining or recycling the steps from the first step to the fourth step until the radioactive activity concentration of the carbon-14-containing waste water is less than the cleaning and controlling level.
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