(12) STANDARD PATENT (11) Application No. AU 2007356815 B2 (19) AUSTRALIAN PATENT OFFICE
(54) Title Single stage purification for uranium refining
(51) International Patent Classification(s) C22B 60/02 (2006.01)
(21) Application No: 2007356815 (22) Date of Filing: 2007.07.24
(87) WIPO No: W009/013759
(43) Publication Date: 2009.01.29 (44) Accepted Journal Date: 2012.08.30
(71) Applicant(s) SECRETARY, DEPARTMENT OF ATOMIC ENERGY
(72) Inventor(s) Shanmugavelu, P.;Dhavamani, D.;Agrawal, Ankur;Bhowmik, A.
(74) Agent / Attorney Griffith Hack, GPO Box 1285, Melbourne, VIC, 3001
(56) Related Art US 4271127 A (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
(19) World Intellectual Property Organization International Bureau lllllllllllllllllllllllllllllllllllll^
(43) International Publication Date PCT (10) International Publication Number 29 January 2009 (29.01.2009) WO 2009/013759 Al
(51) International Patent Classification: (74) Agents: MAJUMDAR, Subhatosh et al.; S. Majumdar & C22B 60/02 (2006.01) Co., 5, Harish Mukherjee Road, Kolkata 700 025 (IN).
(21) International Application Number: (81) Designated States (unless otherwise indicated, for every PCT/IN2007/000305 kind of national protection available): AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA, CH, (22) International Filing Date: 24 July 2007 (24.07.2007) CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, H, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, (25) Filing Language: English IN, IS, JP, KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, (26) Publication Language: English MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, SV, SY, (71) Applicant (for all designated States except US): SEC TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, RETARY, DEPARTMENT OF ATOMIC ENERGY ZM, ZW. [IN/IN]; Government of India, Anushakti Bhavan, Chha- trapati Shivaji Maharaj Marg, Mumbai 400 001 (IN). (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (72) Inventors; and GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, (75) Inventors/Applicants (for US only): BHOWMIK, A. ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), [IN/IN]; Chemical Technology Division, BARC, Trombay, European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, Mumbai 400 085 (IN). SHANMUGAVELU, P. [IN/IN]; FR, GB, GR, HU, IE, IS, IT, LT, LU, LV, MC, MT, NL, PL, Chemical Technology Division, BARC, Trombay, Mum PT, RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, CI, CM, bai 400 085 (IN). DHAVAMANI, D. [IN/IN]; Chemical GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG). Technology Division, BARC, Trombay, Mumbai 400 085 (IN). AGRAWAL, Ankur [IN/IN]; Chemical Technology Published: Division, BARC, Trombay, Mumbai 400 085 (IN). — with international search report IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIN
Ai
(54) Title: SINGLE STAGE PURIFICATION FOR URANIUM REFINING
2009/013759 (57) Abstract: A process for refining yellowcake to produce nuclear grade uranium using a single step precipitation route for the
simultaneous removal of heavy metals, boron and other rare earth metals comprising dissolving the yellowcake in nitric acid under mild agitation and adding hydrogen peroxide at pre-defined pH and temperature to selectively precipitate uranium peroxide hydrate. Also described is a process for producing nuclear grade uranium starting from uranium ore utilizing the above process. w o WO 2009/013759 PCT/IN2007/000305
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SINGLE STAGE PURIFICATION FOR URANIUM REFINING
FIELD OF THE INVENTION The present invention relates to a process for the preparation of nuclear grade pure uranium dioxide, natural metallic uranium and uranium hexafluoride from yellow 5 cake containing boron, rare earth and other metallic impurities. More particularly, the present invention relates to a process for the preparation of pure uranium dioxide that meets the nuclear grade specifications of the equivalent boron content being
less than 4pg/g on uranium basis as per ASTM C - 753-99.
I 10 BACKGROUND AND PRIOR ART Yellowcakes are uranium concentrates, which represent an intermediate step in the processing of uranium ores. Yellowcakes are usually obtained through the milling and chemical processing of uranium ore forming a coarse powder, which is insoluble in water and contains about 60-80% of uranium oxide depending on type of 15 Yellowcakes such as Magnesium Di-uranate, Ammonium Di-uranate or Uranium peroxide. In the process conventionally used within the art, the ore is first crushed to a fine powder by passing the starting raw uranium ore through crushers and grinders to produce the pulped ore. The pulped ore is thereafter processed with concentrated acid or an alkaline solution to leach out the uranium and the eluate is subjected to 20 precipitation of Uranium concentrates that is then filtered and dried to produce yellowcake. This yellowcake usually contains boron, rare earths and other metallic impurities.
The yellowcake thus produced is thereafter converted to nuclear grade pure uranium
25 dioxide, natural metallic uranium and uranium hexafluoride using various processes conventionally known in the art. In one of the known processes i,e Solvent Extraction, the yellowcake is first dissolved in nitric acid and thereafter feed preparation is done to adjust the nitric acid and uranium concentration. This feed is thereafter passed through a multi-stage counter current slurry extractor wherein WO 2009/013759 PCT/IN2007/000305
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uranyl nitrate is extracted using a mixture of 33% tributyl phosphate and kerosene leaving behind impurities in the mother liquor known as raffinate. The organic phase containing pure uranyl nitrate is further subjected to another separation step using de-mineralized water to produce pure uranyl nitrate solution. This pure urnayl nitrate 5 solution is co-precipitated with ammonia to produce ammonium diuranate (ADU), which is thereafter converted to produce nuclear grade uranium dioxide or metallic uranium.
The conventionally known solvent extraction process, which involves the use of 10 carcinogenic materials such as tributyl phosphate, highly inflammable kerosene and hazardous ammonia needs lots of monitoring and safety regulations for industrial . scale operations. This process also produces degraded tributyl phosphate due to reaction with nitric acid and radioactivity, which requires complicated disposal method involving further treatment and incineration facilities, generates lots of solid 15 and liquid wastes containing nitrates which are difficult to dispose off. The generated solid waste contains a preponderance of nitrates, which therefore cannot be recycled for the recovery of uranium without the removal of nitrates. The removal of nitrates from the solid wastes generated requires special treatment steps as nitrate contamination of the ground water may lead to methemoglobinemia and stomach 20 cancer. The conventionally used solvent extraction process is also disadvantageous in that it generates multiple streams of wastes. The liquid waste stream typically contains about 100 ppm of uranium along with the soluble nitrates Which are disposed off in large solar ponds. The disposal of the liquid wastes in the large solar ponds requires large space and a continuous monitoring of the ground water around
25 the solar pond. ,
In another “dry refining process”, the starting yellowcake is directly palletized and reduced with hydrogen to produce uranium dioxide at a temperature between 550 - 650 °C in a fluidized bed reactor. The uranium dioxide is thereafter converted to WO 2009/013759 PCT/IN2007/000305
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uranium tetrafluoride and uranium hexafluoride in the fluidized bed/Flame reactor. - The thus produced uranium hexafluorides are thereafter “refined" using a two-stage pressure distillation process. Further, this process of refining uranium fluorides by pressure distillation is a technically difficult and potentially hazardous process. 5 '
Refining is a process aimed at reducing the harmful impurities to an acceptable level, particularly to meet the nuclear grade specification that the equivalent boron
content (EBC) may not exceed 4pg/g on uranium basis as per ASTM C - 753-99. The process according to the present invention surprisingly brings down the initial
10 EBC of 180 μg/g in the starting yellowcake to about less than 1.0 qg/g of EBC in the
final product.
A further approach for the production of pure uranium grades has been to use purer forms of the starting yellowcakes using hydrogen peroxide for the reduction of Mo, 15 V, P, Zr, As, Ca, Mg, Na, Si and other sulfates to produce purer yellowcakes in the form of uranium peroxide from eluate solutions of sulfate nature compared with Ammonium diuranate and Magnesium diuranate are used as the starting materials. However, it has been found that the yellowcake produced in the form of uranium peroxide using the aforesaid approach also contains substantial levels of rare earth 20 impurities that remain in the yellow cake thus necessitating further refining steps.
Without wishing to be bound by theory, the inventors believe that hitherto, it has been impossible to remove both heavy metals and rare earth impurities such as boron, gadolinium, cadmium, europium and samarium in a single refining step using 25 Hydrogen peroxide as precipitation route because the process involves stringent pH control by the addition of alkaline solutions, which interferes with the simultaneous removal of rare,earth impurities such as boron, gadolinium, cadmium, europium and
samarium in single refining step. WO 2009/013759 PCT/IN2007/000305
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US 4 024 215 describes a process for the preparation of yellowcake, with a reduced content of sodium and vanadium from the eluate. However, the disclosed is not suitable for the removal of the rare earth impurities. Further, the yellowcake produced is further refined using the wet solvent extraction process to produce , 5 nuclear grade uranium, which suffers from the above identified deficiencies.
US 2 770 521 teaches the treatment of sulfated uranium with a peroxide to produce uranium peroxide di-hydrate and separation of relatively pure uranium peroxide. However, the starting material for the process disclosed in this US patent is uranium 10 present in the slag after the magneto-reduction of uranium tetrafluroide, which is already free of the rare earth impurities sought to be removed according to the present invention. A further disadvantage of the process disclosed in this US patent is that the disclosed process requires strict pH control for the complete precipitation of uranium peroxide, which is cumbersome. 15 OBJECTS OF THE INVENTION It is therefore an object of the invention to provide a single step precipitation route for refining yellow cake to produce nuclear grade pure uranium.
20 It is a further object of the invention to provide a process for refining yellowcake that is eco-friendly producing only one waste liquid stream that contains a ppm level of uranium and wherein the level of nitrate impurities is substantially less than that obtained by the solvent wet extraction process. '
25 It is a further object of the present invention to provide a single step precipitation route for refining yellowcake to meet Nuclear Purity Standard as specified by ASTM C 753 - 99 that avoids the use of hazardous and toxic chemicals. WO 2009/013759 PCT/IN2007/000305
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It is a further object of the present invention to provide a process for refining yellowcake to produce nuclear grade pure uranium that permits a simultaneous removal of heavy metals in addition to rare earth metals such as boron, gadolinium, dysprosium, samarium, europium and the like.
5 ' . ' It is a further object of the present invention to provide a process for refining yellowcake to produce nuclear grade pure uranium that brings down the level of rare earth metals such as boron, gadolinium, dysprosium, samarium, europium and the like to less than 0.1 ppm in a single precipitation step followed by washing. 10 It is a further object of the present invention to provide a process for refining yellowcake to produce nuclear grade pure uranium that brings down the Equivalent boron concentration (EBC) of the yellowcake to less than 1.0 microgram per gram of uranium. 15 It is a further object of the present invention to provide a process for refining yellowcake to produce nuclear grade pure uranium that does not require stringent pH control conditions.
20 SUMMARY OF THE INVENTION ' . i A process for refining yellowcake to produce nuclear grade uranium using a single step precipitation route followed by washing for the simultaneous removal of heavy metals, boron and other rare earth metals comprising dissolving the yellowcake in nitric acid under mild agitation and adding hydrogen peroxide at pre-defined pH and 25 temperature to selectively precipitate uranium peroxide hydrate.
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for refining yellowcake to produce nuclear grade uranium using a single step precipitation route followed by washing for the WO 2009/013759 PCT/IN2007/000305
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simultaneous removal of heavy metals, boron and other rare earth metals comprising dissolving the yellowcake in nitric acid under mild agitation and adding hydrogen peroxide at pre-defined pH and temperature to selectively precipitate uranium peroxide hydrate. 5 According to the present invention, the starting yellowcake is preferably magnesium diuranate (MDU), which may be prepared from the uranium ore by processes that are conventionally known in the art. The starting material MDU typically contains
various impurities having an equivalent boron concentration as high as 180 iig/g on
10 uranium basis.
In the process of the present invention, the starting MDU is dissolved in nitric acid to produce crude uranyl nitrate containing all the impurities in dissolved form.
15 In a preferred embodiment, the said nitric acid used has strength of about 2 N to about 6 N.
In a subsequent step of the process of the present invention, uranium peroxide hydrate is selectively precipitated out by the addition of commercial hydrogen 20 peroxide to above uranyl nitrate solution at a predetermined pH. The pH of the solution at the time of addition of hydrogen peroxide is selected such that all the impurities remain in soluble form in the reaction system.
In a preferred embodiment, the commercial hydrogen peroxide is about 30 to 70% 25 w/w. The pH of the reaction system is preferably less than about 2, at which pH, it was surprisingly found that all the impurities were present in the reaction system in soluble form, which enabled precipitation of surprisingly pure uranium peroxide hydrate. WO 2009/013759 PCT/IN2007/000305
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It was surprisingly found that the process outlined above led to the end product i.e. uranium peroxide hydrate that had a substantially reduced equivalent boron
concentration less than 1.0 pg/g of EBC, which is well below the specification
depicted in ASTM C 753 - 99. It was also found that the process herein described 5 led to a simultaneous reduction of the heavy metal as well as rare earth metal content such that of gadolinium, cadmium, europium, samarium in addition to boron and other heavy metals such as iron, nickel, cobalt, calcium and magnesium in one refining step, which was hitherto not possible using hydrogen peroxide precipitation route. 10 A qualitative analysis of the refined uranium peroxide hydrate according to the process described herein presented the following results.
Elements Impurity in MDU Impurity in Uranium (pg/g of U) Peroxide hydrate prepared according to the invented process (gg/gofU) B 20 0.1 (decontamination factor = 200) Gd 29 0.04 (decontamination factor = 750) Cd 3.1 <0.1 Eu 18 <0.1 Sm 2.8 <0.1 Fe 6000 22 Mg 82200 19 Ca ,12500 77
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The present inventors have also found that completion of precipitation as well as the efficiency of refining depended on the stoichiometric ratios of the reactants, system . pH and temperature. While the role of pH in the purity of the final product is not clear, the present inventors believe that the reaction according to the invented 5 process leads to an in-situ formation of nitric acid, which increases the tendency for · the precipitated end product to get dissolved back favoring a reverse reaction. A careful monitoring of the pH to below 2 presumably strikes balance between the prevention of co-precipitation of impurities along with uranium peroxide hydrate, and a comparatively slow reverse reaction favoring a low dissolved uranium peroxide 10 hydrate content in the filtrate. It is also believed that a . low temperature of the reaction system favors lower uranium content in the solution as the solubility of uranium peroxide hydrate in nitric acid is found to be low at room temperature. This ensures that a concentration of uranium content in the filtrate could be maintained below 300 ppm. \
15 - In a further optional embodiment, the dissolved uranium content (less than 300 ppm) could be optionally further reduced to less than 50 ppm by further adding hydrogen peroxide over a sufficient time period to allow delayed precipitation of uranium peroxide hydrate with addition of suitable flocculants like INDFLOC or by Ion 20 Exchange with suitable cation or anion based resins. Thus, it was found that the overall uranium content loss from the system could be kept at as low as 20- 50 ppm which is well below the overall loss of uranium content in the conventional solvent extraction process.
25 The suspended uranium content in the system could be possibly be also removed by ' micro filtration after heavy metal removal.
In a preferred embodiment, the amount of commercial hydrogen peroxide added was 1.5-6 times the stoichiometric amount of the uranium in the starting MDU. The WO 2009/013759 PCT/IN2007/000305
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temperature at which hydrogen peroxide is added preferably varies from about 15 to about 30°C to produce relatively pure uranium peroxide hydrate.
The reaction according to the invented process is instantaneous and is preferably. 5 carried out in a stainless steel container under controlled addition of hydrogen peroxide. The entire system is kept under mild turbulence by turbine type agitator at 150 - 200 rpm to complete the precipitation process. The yellow colored uranium peroxide thus produced needs a proper separation from the residual solution, which is carried out in a neutche filter backed up by a vacuum pump or by centrifuge 10 followed by de-mineralized water washing cycles. If was found that preferably, two washing cycles with de-mineralized water was sufficient to produce uranium peroxide hydrate having desired purity levels.
, The washed solid is fed to a co-current spray drier to remove the additional moisture 15 content at an inlet air temperature of 200 - 300°C and an exhaust temperature of 100 - 130°C. The dried powder in the size range of 2 - 10 micron was the end
product obtained by the herein described process.
An advantage of the process according to the present invention is that there is a
20 single waste stream (liquid) that is more convenient to handle and dispose off vis-a vis the solid and the liquid waste streams conventionally produced in the state of the art. This wastewater stream was found to carry a few ppm of uranium, which could be micro filtered to discharge a very clear permeate as effluent containing only soluble rare earths.
25 / ■ . ' Another significant advantage of the process according to the present invention is that the entire process requires only nitric acid and commercial grade hydrogen , peroxide as the reaction chemicals thereby eliminating the need for tributyl WO 2009/013759 PCT/IN2007/000305
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phosphate, kerosene, sodium carbonate, ammonia and other waste treatment chemicals, which are conventionally used in the solvent extraction process.
The present process therefore provides an efficient refining of yellowcake in a much 5 more simple way, reducing load of waste streams, chemicals inventory and offering much more in-built safety features. The process is also compact, both capital cost and running cost saving and could be integrated to milling operation thus eliminating requirement of separate refining facility.
10 The invention shall now be described with reference to the following specificz examples. It should be noted that the example(s) appended below illustrate rather ' I ‘ than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In the claims, the word ‘comprising’ does not exclude the presence of other elements 15 or steps than those listed in a claim. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
Other than in the operating examples provided hereunder, or where otherwise
20 indicated, all numbers expressing quantities of ingredients or reaction conditions are to be understood as being modified in all instances by the term “about".
EXAMPLE 1 MDU powder was dissolved in nitric acid (2 - 6 N) at 80 - 90°C and the uranium
25 content in initial solution kept at 250 - 300 g/lit and free acidity up to maximum of 3N. The solution was then diluted with DM water to keep uranium concentration in the range of 10 - 50 g/lit. Commercial hydrogen peroxide in the concentration range of 30 - 70% (w/w) was then gradually added to the crude uranyl nitrate solution at temperature range of 15 - 30°C. A turbine type agitator kept the whole system in 2012
11 Aug
mild turbulence (150 - 200 rpm) so as to maintain uniform reaction as well as 02 unhindered growth of particles. The whole reaction was carried out in SS container.
The yellow colored uranium peroxide hydrate precipitated out instantaneously and was subjected to filtration. This part required efficient separation of solid and liquid 5 followed by DM water washing cycles . The washed cake was collected and fed to a co-current spray drier (in S No. 5* & 6* below) at inlet air temperature of 200 - 300°C and exhaust air temperature of 100 - 130°C in effect to a dry granular product. The
2007356815 filtrate contained 150 - 300 ppm of dissolved uranium content, which was further brought down to less than 50 ppm before discharging to solar pond by proper pH 10 adjustment, and addition of little quantity of hydrogen peroxide and flocculants causing delayed precipitation.
Exp No. Solution U(gm) Quantity of DM wash Total EBC Volume (ml) H202 (ml) water (ml) 1 400 20 17.2 3000 <1 2 1500 75 112.5 1400 <1 3 1500 75 150 1400 <1 4 20000 1000 6000 7500 <1 5* 20000 1000 900 12000 <1 6* 90000 5000 6000 35000 <1
In the claims which follow and in the preceding description of the invention, except 15 where the context requires otherwise due to express language or necessary implication, the word ''comprise” or variations such as "comprises” or "comprising” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
35598W.1 (GHMaaer») P82V41AU 11a
It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
5558820,1 (GHMaCors) P82W1AU 2012
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CLAIMS 02 1. A process for refining crude yellow cake containing significant levels of rare
earths like Gadolinium, Europium, Samarium, and Dysprosium and other elements like Boron, Cadmium and Iron to produce nuclear grade uranium, 5 using a single step precipitation route for simulataneous removal of above said impurities, comprising of dissolving the yellow cake in nitric acid under mild agitation and adding hydrogen peroxide at pre-defined pH and
2007356815 temperature to selectively precipitate uranium peroxide hydrate, having total equivalent boron content (EBC) less than 4.0 //g/g on U weight basis and 10 individual impurity elements as per ASTM C 753.
2. A process as claimed in claim 1, wherein said crude yellow cake is Magnesium Diurante (containing 58-72% of uranium calculated as U3O8), having said impurity elements as high as 180 z/g/g on U weight basis as total 15 equivalent boron content.
3. A process as claimed in claim 1 or claim 2, wherein the uranium concentration of said yellow cake dissolved in nitric acid is in the range of 10- 50g /lit. 20 4. A process as claimed in any preceding claim, wherein hydrogen peroxide is added to uranyl nitrate solution at a pH selected such that all the impurities remain in soluble form in the reaction system.
25 5. A process as claimed in claim 4, wherein said pH is less than 2.
6. A process as claimed in claim 1, wherein said pH is not controlled during precipitation by addition of any chemical.
30 7. A process as claimed in claim 6, wherein said pH is less than 2.
1550020.1 (GHMaaers)Pe2941AU 2012
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02 8. A process as claimed in any preceding claim, wherein said commercial hydrogen peroxide is in the range of 30 to 70% w/w.
5 9. A process as claimed in any preceding claim, wherein the amout of commercial hydrogen peroxide added was 1.5-6 times the stoichiometric amount of the starting MDU which is equivalent of U : H2O2 as 1:3 to 1:12 wherein U in MDU is 50-60%. 2007356815
10 10. A process as claimed in any preceding claim, wherein the temperature at which hydrogen peroxide is added in the range of 15 to 30°C.
11. A process as claimed in any preceding claim, wherein said refining is carried out under mild turbulence by turbine type agitator at 150 - 200 rpm. 15 12. A process as claimed in any preceding claim, wherein uranium peroxide hydrate produced is separated from the residual solution using a filter followed by one or more de-mineralized water washing cycles.
20 13. A process as claimed in claim12, which comprises two water-washing cycles.
14. A process as claimed in claim 12 or claim 13, wherein said washed solid is fed to a co-current spray drier to remove the additional moisture content at an inlet air temperature of 200 - 300°C and an exhaust temperature of 100 - 25 130°C.
15. A process as claimed in claims 9-11, wherein the particle size of the end product is in the size range of 2 - 10 μ.
3SSU20.1 (GHMottorslPCMIAU 2012
14 Aug 16. A process for refining crude yellow cake containing significant levels of rare 02 earths like Gadolinium, Europium, Samarium and Dysprosium and other
elements like Boron, Cadmium and Iron to produce nuclear grade uranium, using a single step precipitation route for simultaneous removal of above said 5 impurities, substantially as herein described with reference to the Example. 2007356815
3550620.1 (6HMaem)P82M1AU