Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition
In the world, it is planned to produce promising for the manufacture of radiopharmaceuticals of radioisotope copper-67 by the reaction of its production from zinc-68 under the influence of γ-radiation on an electron accelerator. The next major issue is the separation of copper and zinc. Extraction,...
Збережено в:
| Опубліковано в: : | Вопросы атомной науки и техники |
|---|---|
| Дата: | 2020 |
| Автори: | , , |
| Формат: | Стаття |
| Мова: | Англійська |
| Опубліковано: |
Національний науковий центр «Харківський фізико-технічний інститут» НАН України
2020
|
| Теми: | |
| Онлайн доступ: | https://nasplib.isofts.kiev.ua/handle/123456789/194545 |
| Теги: |
Додати тег
Немає тегів, Будьте першим, хто поставить тег для цього запису!
|
| Назва журналу: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Цитувати: | Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition / O.I. Azarov, V.O. Bocharov, O.F. Stoyanov // Problems of atomic science and tecnology. — 2020. — № 3. — С. 177-179. — Бібліогр.: 11 назв. — англ. |
Репозитарії
Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1860239745053884416 |
|---|---|
| author | Azarov, O.I. Bocharov, V.O. Stoyanov, O.F. |
| author_facet | Azarov, O.I. Bocharov, V.O. Stoyanov, O.F. |
| citation_txt | Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition / O.I. Azarov, V.O. Bocharov, O.F. Stoyanov // Problems of atomic science and tecnology. — 2020. — № 3. — С. 177-179. — Бібліогр.: 11 назв. — англ. |
| collection | DSpace DC |
| container_title | Вопросы атомной науки и техники |
| description | In the world, it is planned to produce promising for the manufacture of radiopharmaceuticals of radioisotope copper-67 by the reaction of its production from zinc-68 under the influence of γ-radiation on an electron accelerator. The next major issue is the separation of copper and zinc. Extraction, ion exchange and thermal distillation of zinc have already been studied in detail. Co-precipitation of copper with low zinc and thermal distillation of organic compounds of metals is promising.
У світі планується виробляти перспективний для виготовлення радіофармпрепаратів радіоізотоп міді-67 по реакції ії одержання з цинку-68 під впливом γ-випромінювання на прискорювачі електронів. Наступною за значенням проблемою є розділення міді і цинку. Вже докладно досліджені екстракція, іонний обмін та термічна відгонка цинку. Перспективним є співосадження міді з малою кількістю цинку і термічна відгонка органічних сполук металів.
В мире планируется производить перспективный для приготовления радиофармпрепаратов радиоизотоп меди-67 по реакции еe получения из цинка-68 под действием γ-излучения на ускорителе электронов. Следующей по значению проблемой является разделение меди и цинка. Уже подробно исследованы экстракция, ионный обмен и термическая отгонка цинка. Перспективным является соосаждение меди с малым количеством цинка и термическая отгонка органических соединений металлов.
|
| first_indexed | 2025-12-07T18:28:40Z |
| format | Article |
| fulltext |
ISSN 1562-6016. ВАНТ. 2020. №3(127) 177
RESEARCH ON COPPER-67 SEPARATION OBTAINED
BY PHOTO-NUCLEAR FROM ZINC OF NATURAL COMPOSITION
O.I. Azarov, V.O. Bocharov, O.F. Stoyanov
National Science Center “Kharkov Institute of Physics and Technology”, Kharkiv, Ukraine
E-mail: bocharov@kipt.kharkov.ua
In the world, it is planned to produce promising for the manufacture of radiopharmaceuticals of radioisotope
copper-67 by the reaction of its production from zinc-68 under the influence of γ-radiation on an electron accelera-
tor. The next major issue is the separation of copper and zinc. Extraction, ion exchange and thermal distillation of
zinc have already been studied in detail. Co-precipitation of copper with low zinc and thermal distillation of organic
compounds of metals is promising.
PACS: 8255.+e
INTRODUCTION
Copper-67 is a β-emitter with an average energy of
141 keV and a half-life of 61.8 h, accompanied by γ-
radiation of 91, 93, and 185 keV, it is produced by the
reaction of 68Zn (γ, p) 67Cu on the electron accelerator
at their energy 30…60 MeV and even 25 MeV. The use
of an electron accelerator to produce copper-67 reduces
the amount of radioactive waste. Copper-67 and its de-
cay product 67Zn are not acutely toxic. These character-
istics make it suitable for use in diagnosis and treat-
ment. But there are still no methods of industrial pro-
duction of this isotope.
Almost comprehensive data on copper production at
that time, including the separation of copper and zinc,
were given in the article [1]. In the following years,
Ehst and his staff developed a means of thermal separa-
tion of copper from irradiated zinc [2] at an energy of
40…50 MeV with a tantalum converter. Distillation of
zinc was carried out under vacuum at 500…700C. In
this way, a copper concentrate, which needs further
purification, was obtained. Significant requirements for
the material of the vessel from which the distillation
was carried out take place, it is necessary that it does
not contaminate metals and they do not stick to it, and
also have a reasonable price. Only fused aluminum ox-
ide (leucosapphire) meets these requirements. The so-
phisticated equipment used for thermal separation of
copper from zinc ingot inhibits the introduction of cop-
per-67 isotope for the manufacture of radiopharmaceu-
ticals. If you think about it, you can suggest other ways
of separating ultra-low concentrations of copper from
zinc. The classical methods are liquid extraction with
organic solvents and ion exchange. In these two ways,
extraction is easier, since ion exchange requires more
labor and in the end we get the final product distributed
in a large volume of water. Consideration should be
given to such methods as the co-precipitation of copper
with zinc compounds and the distillation of our metals
in the form of organic compounds.
1. LIQUID COPPER EXTRACTION
Some authors have used sodium diethyldithio-
carbamate (NaDTC) to extract copper from zinc [3].
From the solution of zinc salts copper is extracted into
carbon tetrachloride at pH 4.5…5.5, at such a pH is not
formed the basic zinc salts. The molar ratio of copper:
NaDTC 1: 3 is sufficient for complete extraction of
copper from a solution containing 20 g/l zinc. After
dissolving a zinc sample (~ 20 g) containing 2…15 μg
of copper, the solution in the separating funnel is neu-
tralized with ammonia to pH 4.5…5, 20 ml of a 20%
solution of ammonium citrate for masking iron, 1 ml of
0.1% aqueous NaDTC solution and 10 ml CCl4 , vigor-
ously shaken for 2 min. In the second work of the same
authors [4] it is stated that when the content of copper
in zinc 1·10-5% even 1.5…2-fold excess of NaDTC
against stoichiometric is sufficient. The extraction time
is only 10 min.
The above quoted authors did not indicate that it ex-
tracts a certain amount of zinc with NaDTC copper. In
[5] it is shown that even all reagents contain copper,
and when determining 10-7% of copper in zinc it is nec-
essary to further clean the reagents from copper. For
example, the original 0.2M NaDTC solution was shak-
en with chloroform. The difference with previous pub-
lications [3, 4] in the use of chloroform (instead of car-
bon tetrachloride) as solvent and extraction from slight-
ly acidic medium (pH 4.0…4.5) exists.
Dithizone is also widely used as a 0.01…0.001%
solution in carbon tetrachloride only. In one of the pio-
neering works [6], radioactive copper was extracted
with a 0.001% solution at a pH of 1…1.2 three times,
the combined extracts were washed with 0.1 M hydro-
chloric acid, the extract was evaporated, and copper
dithizonate in the dry residue was destroyed at 500C.
The reference [1] cites a work in which the accompany-
ing zinc after the destruction of dithizonate in acidic
medium with hydrogen peroxide was absorbed by a
strong basic anion exchanger in the chloride form (re-
generated 6 M HCl).
In the work with copper also used diantipyril-
methane [7]. When the acidity of the aqueous solution
of 2.5…3 M HCl extract Cu2+ does not exceed 10%, so
we used chloroform extraction of the complex of
monovalent copper (after reduction of Cu2+), which
completely goes into the organic phase in a wide range
of acidity of the medium: from 0.5 to 6 M HCl, the
concentration of chloride ions should not be lower than
2…3 M, the extraction is carried out twice.
Re-extraction is carried out with alkaline water
mixed with hydrogen peroxide to oxidize copper. In the
second work of the analysts of this school [8] it was
found that 99% of copper is extracted from iodide solu-
tions (3% by KI) with 5-fold excess of diantipyril-
methane. In this case, the monovalent copper is also
extracted, since the iodide ion is a strong reducing
agent. It is stated that zinc interferes with the extraction
ISSN 1562-6016. ВАНТ. 2020. №3(127) 178
of copper from the chloride system, probably bromides
and iodides will also interfere with the presence of zinc.
We used diantipyrylpropylmethane (DAPM) derivative
of diantipyrylmethane to extract copper. Our analysis
showed that 1 g of zinc brand "pure for analysis" con-
tains 15.4 μg of copper or 1.54·10-3%, in some cases,
the copper content reached 9·10-3%. Based on general
considerations and previous experiments, we chose
following the extraction conditions: zinc concentration
up to 2 M, sulfuric acid 1 M, potassium iodide 0.1 M,
DAPM 0.02 M in chloroform. Usually used volumes of
aqueous solution and chloroform with reagent. From
chloroform, copper was extracted with slightly alkaline
water with hydrogen peroxide as above [7] and the pH
of the water should not be below 6. But the tests
showed that a considerable amount of zinc is extracted
with the copper, even exceeding the amount of copper
many times over. Copper is probably extracted from the
sulfuric acid medium in the form of an ionic associate
(LH) [CuI2], where LH+ is a protonated DAPM mole-
cule. Apparently, besides such an associate, charged
particles with copper are formed, which do not pass into
the organic phase. In a separate experiment, the copper
content of the aqueous reextract was 0.024 mg/l and at
the same time zinc in the same sample was 0.631 mg/l.
The extraction of copper from an aqueous solution of
zinc salt was only 2…3%.
2. COPPER COPRECIPITATION
To extract copper from zinc, researchers used co-
precipitation with hard-soluble zinc phosphate [9]. Zinc
phosphate was precipitated at pH 3, and it was found
that the greater the zinc phosphate crystals, the less
copper was precipitated. Probably the mechanism of co-
deposition of such copper is either part of the crystals or
sorbed by the surface of the crystal. In any case, the
smaller the size of the crystals, the more copper co-
precipitates. To reduce the size of the crystals, urea was
added to the zinc sulfate solution. Copper from the dis-
solved precipitate was extracted at pH 9…10 with car-
bon tetrachloride as diethyldithiocarbamate. Apparently
the disappointing results were obtained that the method
of determining copper in zinc sulfate did not work.
The authors of article [10] emphasize that the de-
termination of copper is less than 1 mg/l in solutions
where there are other metals at a concentration of
100…150 g/l complex problem, but they solved it quite
simply, co-planted copper with diethyldithiocarbamates
nickel and cobalt. The authors neutralized the sample to
pH 1…5 with ammonia and added an aqueous reagent
solution. The precipitate was dissolved in a mixture of
hydrochloric and nitric acids and analyzed. Copper also
displaces zinc from the diethyldithiocarbamate complex
and is therefore deposited first. We used NaDTC to
deposit copper. It is known that the reagent dissolves
well in water (3.5 g (C5 H10 NNaS2·3H2O) per 100 ml).
Metallic zinc (10 g) was dissolved in hydrochloric acid
(37 ml, 2 M), 2 drops of nitric acid were added to ac-
celerate dissolution of the residues. We removed the
excess acid, bringing the residue to 50 ml with pH 4.5
(NH3). To 20 ml of this solution was added 1 ml of sat-
urated aqueous NaDTC solution, a white precipitate
precipitated, which then turned a little yellow. The filter
cake was dissolved in 5 ml HCl (2M) + one drop of
HNO3, evaporated and redissolved in HCl. Excess zinc
was removed on a very basic anion exchanger, after
ionic purification the copper concentration was
0.4…0.5 mg/l and zinc 5.3…5.9 mg/l. We compared
different methods of extracting copper from a concen-
trated solution of zinc salt: at ion-exchange separation
on a strongly basic anion exchanger AV-17, the zinc
residue was most often ~ 50…60 mg/l, when extracted
from NaDTC the zinc residue was 24…27 mg/l, when
extracted with DAPM 3.6 mg/l. Thus, when perform-
ing the operation of separation into one stage, the
DAPM reagent is most effective.
3. PROSPECTS OF USE OF VARIOUS
COPPER AND ZINC COMPOUNDS FOR
THEIR DIVISION
Mosher and Sievers' monograph indicates that cop-
per with trifluoroacetylacetone forms a volatile com-
plex that can be dispersed without decomposition, with
the zinc complex being destroyed [11]. We tested the
properties of copper and zinc acetylacetonates after
their synthesis. Copper forms a complex of blue color
very easily with almost 100% yield, the yield of color-
less zinc acetylacetonate is several tens of percent. The
optimum pH for the synthesis of copper acetylacetonate
is 5.4, and for zinc is 8.9. Acetyl acetonates of copper
and zinc were obtained by reacting aqueous solutions of
metal sulfates with acetylacetone by adding ammonia
and ethyl alcohol. According to the literature, acety-
lacetonate of copper is distilled at 236C with decom-
position, according to our data, the constancy of mass
remains up to 175C. Zinc acetylacetonate as if distilled
at 350C with decomposition, but according to our ex-
perimental data, it begins to decompose already at
80C. More volatile complexes give fluorinated β-
diketones.
CONCLUSIONS
Distillation as a way of separating zinc copper is a
promising thing. Distillation of volatile copper com-
pounds and possibly zinc in the future can be intro-
duced to simplify the separation apparatus and condi-
tions. Co-precipitation, ion exchange, and extraction
remain important additional methods for separating
copper from the zinc matrix.
REFERENCES
1. N.A. Smith, D.L Bowers, D.A. Ehst. The produc-
tion, separation, and use of 67Cu for radioimmuno-
therapy: a review // Applied Radiation and Isotopes.
2012, v. 70, p. 2377-2383.
2. D.A. Ehst, J.L. Willit. Methods for producing Cu-67
radioisotope with use of a ceramic capsule for med-
ical applications // US Patent No. 9312037 B2,
Apr.12, 2016.
3. K.B. Kladnitskaya, A.N. Grisevich. To the determi-
nation of copper in cadmium and zinc by diethyldi-
thiocarbamate // Ukr. Chem. Jorn. 1961, v. 27, № 6,
p. 803-807.
4. A.N. Grisevich, K.B. Kladnitskaya. A quick method
for detecting small amounts of copper in zinc and
ISSN 1562-6016. ВАНТ. 2020. №3(127) 179
cadmium // Factory Laboratory. 1961, v. 27, № 11,
p. 1343-1328.
5. A.K. Babko, L.I. Dubovenko. Chemiluminiscent
determination of copper in zinc and high purity al-
cali // Factory Laboratory. 1964, v. 30, № 11,
p. 1325-1328.
6. F.F. Dyer, G.W. Leddicotte. The radiochemistry of
copper // Oak Ridge National Laboratory. April
1961, p. 42-43.
7. V.H. Antonova, I.P. Zhivopiscev Copper determina-
tion // Scientific notes of Perm University. 1974,
№ 324, p. 57-59.
8. Y.A. Mahnev, M.I. Degtev. Chemical spectral de-
termination of copper using three-phase extracting
systems // Org. reagents in analytical chemistry.
Perm. 1980, Issue 3, p. 69-73.
9. V.T. Chuiko, N.I. Reva. The coprecipitation of trace
copper with zinc phosphate from a solution of zinc
sulfate // Ukr. Chem. Journ. 1968, v. 34, № 2,
p. 193-195.
10. D.F. Makarov, I.S. Ostapchuk. Determination of
cobalt in nickel-cobalt sulfate solutions // Factory
Laboratory. 2003, v. 69, № 11, p. 22.
11. R. Moshier, R. Sives. Gas chromatography of metal
chelates. M.: “Mir”, 1967, 175 p.
Article received 18.01.2020
ИССЛЕДОВАНИЯ ПО ВЫДЕЛЕНИЮ МЕДИ-67, ПОЛУЧЕННОЙ ФОТОЯДЕРНЫМ СПОСОБОМ
ИЗ ЦИНКА ПРИРОДНОГО СОСТАВА
А.И. Азаров, В.А. Бочаров, А.Ф. Стоянов
В мире планируется производить перспективный для приготовления радиофармпрепаратов радиоизотоп
меди-67 по реакции еe получения из цинка-68 под действием γ-излучения на ускорителе электронов.
Следующей по значению проблемой является разделение меди и цинка. Уже подробно исследованы
экстракция, ионный обмен и термическая отгонка цинка. Перспективным является соосаждение меди с
малым количеством цинка и термическая отгонка органических соединений металлов.
ДОСЛІДЖЕННЯ ПО ВИДІЛЕННЮ МІДІ-67, ОДЕРЖАНОЇ ФОТОЯДЕРНИМ СПОСОБОМ
З ЦИНКУ ПРИРОДНОГО СКЛАДУ
О.І. Азаров, В.О. Бочаров, О.Ф. Стоянов
У світі планується виробляти перспективний для виготовлення радіофармпрепаратів радіоізотоп міді-67
по реакції ії одержання з цинку-68 під впливом γ-випромінювання на прискорювачі електронів. Наступною
за значенням проблемою є розділення міді і цинку. Вже докладно досліджені екстракція, іонний обмін та
термічна відгонка цинку. Перспективним є співосадження міді з малою кількістю цинку і термічна відгонка
органічних сполук металів.
|
| id | nasplib_isofts_kiev_ua-123456789-194545 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1562-6016 |
| language | English |
| last_indexed | 2025-12-07T18:28:40Z |
| publishDate | 2020 |
| publisher | Національний науковий центр «Харківський фізико-технічний інститут» НАН України |
| record_format | dspace |
| spelling | Azarov, O.I. Bocharov, V.O. Stoyanov, O.F. 2023-11-27T13:38:37Z 2023-11-27T13:38:37Z 2020 Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition / O.I. Azarov, V.O. Bocharov, O.F. Stoyanov // Problems of atomic science and tecnology. — 2020. — № 3. — С. 177-179. — Бібліогр.: 11 назв. — англ. 1562-6016 PACS: 8255.+e https://nasplib.isofts.kiev.ua/handle/123456789/194545 In the world, it is planned to produce promising for the manufacture of radiopharmaceuticals of radioisotope copper-67 by the reaction of its production from zinc-68 under the influence of γ-radiation on an electron accelerator. The next major issue is the separation of copper and zinc. Extraction, ion exchange and thermal distillation of zinc have already been studied in detail. Co-precipitation of copper with low zinc and thermal distillation of organic compounds of metals is promising. У світі планується виробляти перспективний для виготовлення радіофармпрепаратів радіоізотоп міді-67 по реакції ії одержання з цинку-68 під впливом γ-випромінювання на прискорювачі електронів. Наступною за значенням проблемою є розділення міді і цинку. Вже докладно досліджені екстракція, іонний обмін та термічна відгонка цинку. Перспективним є співосадження міді з малою кількістю цинку і термічна відгонка органічних сполук металів. В мире планируется производить перспективный для приготовления радиофармпрепаратов радиоизотоп меди-67 по реакции еe получения из цинка-68 под действием γ-излучения на ускорителе электронов. Следующей по значению проблемой является разделение меди и цинка. Уже подробно исследованы экстракция, ионный обмен и термическая отгонка цинка. Перспективным является соосаждение меди с малым количеством цинка и термическая отгонка органических соединений металлов. en Національний науковий центр «Харківський фізико-технічний інститут» НАН України Вопросы атомной науки и техники Application of accelerators in radiation technologies Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition Дослідження по виділенню міді-67, одержаної фотоядерним способом з цинку природного складу Исследования по выделению меди-67, полученной фотоядерным способом из цинка природного состава Article published earlier |
| spellingShingle | Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition Azarov, O.I. Bocharov, V.O. Stoyanov, O.F. Application of accelerators in radiation technologies |
| title | Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition |
| title_alt | Дослідження по виділенню міді-67, одержаної фотоядерним способом з цинку природного складу Исследования по выделению меди-67, полученной фотоядерным способом из цинка природного состава |
| title_full | Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition |
| title_fullStr | Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition |
| title_full_unstemmed | Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition |
| title_short | Research on copper-67 separation obtained by photo-nuclear from zinc of natural composition |
| title_sort | research on copper-67 separation obtained by photo-nuclear from zinc of natural composition |
| topic | Application of accelerators in radiation technologies |
| topic_facet | Application of accelerators in radiation technologies |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/194545 |
| work_keys_str_mv | AT azarovoi researchoncopper67separationobtainedbyphotonuclearfromzincofnaturalcomposition AT bocharovvo researchoncopper67separationobtainedbyphotonuclearfromzincofnaturalcomposition AT stoyanovof researchoncopper67separationobtainedbyphotonuclearfromzincofnaturalcomposition AT azarovoi doslídžennâpovidílennûmídí67oderžanoífotoâdernimsposobomzcinkuprirodnogoskladu AT bocharovvo doslídžennâpovidílennûmídí67oderžanoífotoâdernimsposobomzcinkuprirodnogoskladu AT stoyanovof doslídžennâpovidílennûmídí67oderžanoífotoâdernimsposobomzcinkuprirodnogoskladu AT azarovoi issledovaniâpovydeleniûmedi67polučennoifotoâdernymsposobomizcinkaprirodnogosostava AT bocharovvo issledovaniâpovydeleniûmedi67polučennoifotoâdernymsposobomizcinkaprirodnogosostava AT stoyanovof issledovaniâpovydeleniûmedi67polučennoifotoâdernymsposobomizcinkaprirodnogosostava |