CN1922110A - Liquid stock for dropping, method for preparing liquid stock for dropping, method for preparing uranyl nitrate solution, and method for preparing polyvinyl alcohol solution - Google Patents
Liquid stock for dropping, method for preparing liquid stock for dropping, method for preparing uranyl nitrate solution, and method for preparing polyvinyl alcohol solution Download PDFInfo
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- CN1922110A CN1922110A CNA2004800420341A CN200480042034A CN1922110A CN 1922110 A CN1922110 A CN 1922110A CN A2004800420341 A CNA2004800420341 A CN A2004800420341A CN 200480042034 A CN200480042034 A CN 200480042034A CN 1922110 A CN1922110 A CN 1922110A
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- Prior art keywords
- polyvinyl alcohol
- stock liquid
- solution
- uranyl nitrate
- particle
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Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 171
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 171
- 238000000034 method Methods 0.000 title claims abstract description 89
- 229910002007 uranyl nitrate Inorganic materials 0.000 title claims abstract description 82
- 235000015073 liquid stocks Nutrition 0.000 title 2
- 239000007788 liquid Substances 0.000 claims abstract description 144
- 239000002245 particle Substances 0.000 claims abstract description 133
- ZAASRHQPRFFWCS-UHFFFAOYSA-P diazanium;oxygen(2-);uranium Chemical compound [NH4+].[NH4+].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[U].[U] ZAASRHQPRFFWCS-UHFFFAOYSA-P 0.000 claims abstract description 79
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 83
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 47
- 229910017604 nitric acid Inorganic materials 0.000 claims description 47
- 238000002360 preparation method Methods 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 42
- WZECUPJJEIXUKY-UHFFFAOYSA-N [O-2].[O-2].[O-2].[U+6] Chemical compound [O-2].[O-2].[O-2].[U+6] WZECUPJJEIXUKY-UHFFFAOYSA-N 0.000 claims description 35
- 229910000439 uranium oxide Inorganic materials 0.000 claims description 35
- 229910052770 Uranium Inorganic materials 0.000 claims description 26
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 230000002829 reductive effect Effects 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 74
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 54
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 description 35
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 35
- 239000007864 aqueous solution Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 29
- 229910021529 ammonia Inorganic materials 0.000 description 27
- JCMLRUNDSXARRW-UHFFFAOYSA-N trioxouranium Chemical compound O=[U](=O)=O JCMLRUNDSXARRW-UHFFFAOYSA-N 0.000 description 26
- IQWPWKFTJFECBS-UHFFFAOYSA-N O=[U](=O)O[U](=O)(=O)O[U](=O)=O Chemical compound O=[U](=O)O[U](=O)(=O)O[U](=O)=O IQWPWKFTJFECBS-UHFFFAOYSA-N 0.000 description 23
- 239000000463 material Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 230000002950 deficient Effects 0.000 description 7
- 230000008719 thickening Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003758 nuclear fuel Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- YCZZQSFWHFBKMU-UHFFFAOYSA-N [5-(hydroxymethyl)oxolan-2-yl]methanol Chemical compound OCC1CCC(CO)O1 YCZZQSFWHFBKMU-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Abstract
The object of the present invention is to provide a feedstock liquid, from which fuel kernels with good quality can be produced, and a method of preparing the feedstock liquid. The present invention provides a feedstock liquid with a viscosity from 4.0 x 10 -2 to 6.5 x 10 -2 Pas at 15 DEG C, for the production of ammonium diuranate particles. The present invention also provides a method of preparing a feedstock liquid used for the production of ammonium diuranate particles, which includes mixing a uranyl nitrate solution and tetrahydrofurfuryl alcohol to produce a uranyl nitrate mixture, dissolving polyvinyl alcohol in water to produce an aqueous polyvinyl alcohol solution, mixing the aqueous polyvinyl alcohol solution with tetrahydrofurfuryl alcohol to produce a polyvinyl alcohol solution, and mixing the uranyl nitrate mixture with the polyvinyl alcohol solution.
Description
Technical field
The present invention relates to stock liquid, prepare the method for stock liquid, the method for preparing the method for uranyl nitrate solution and prepare polyvinyl alcohol solution.More specifically, the present invention relates to contain the stock liquid of uranyl nitrate, it is suitable for preparing the ammonium diuranate particle that has good sphericity and be used to make high-temperature gas reactor fuel, relate to the preparation method of this stock liquid and relate to the method for preparing uranyl nitrate solution and polyvinyl alcohol solution, wherein said these two kinds of liquid all are used to prepare described stock liquid.
Background technology
The high-temperature gas reacting appliance device nuclear core that responds is introduced the fuel that is used for this high-temperature gas reactor in this reactor nuclear core, this reactor nuclear core is by having big thermal capacity and keeping the graphite manufacturing in shape of its crystalline structure at high temperature.Described high-temperature gas reactor uses the gas of helium for example as coolant gas, and this is considered to safe, even because helium does not at high temperature react yet.The use of helium makes and can safely coolant gas be taken away, even when the temperature around the coolant gas outlet is very high.Therefore, be heated to about 1000 ℃ of pyritous coolant gas and in a lot of fields, be used as thermal source, for example hydrogen manufacturing and chemical plant, and power station.
The fuel that is used for the high-temperature gas reactor typically comprises the coat of fuel kernel and the described fuel kernel of covering.Described fuel kernel is the small-particle of the about 350-650 μ of diameter m, prepares by the physical condition that uranium dioxide is sintered into similar pottery.
Described coat generally includes the coarctate sub-coat of concentric layer.When described coat had four sub-coats, they were called as " the first sub-coat ", " the second sub-coat ", " the 3rd sub-coat " and " the 4th sub-coat " from the sub-coat of adjacency fuel kernel.The about typically 500-1000 μ of the particulate diameter m that comprises fuel kernel and four sub-coats.
Described fuel kernel can utilize as follows and be used to prepare the device fabrication of ammonium diuranate particulate.At first, the uranium oxide of powder type is dissolved in the nitric acid, this has produced uranyl nitrate solution.Then, this uranyl nitrate solution is mixed with pure water, thickening material and other chemical that needs, and stir the mixture.Obtain the stock liquid that will drip by this method.This stock liquid is stored in the stock liquid storage tank.With the temperature that this stock liquid that so prepares is cooled to be scheduled to, regulate its viscosity, then it is transferred in the dropping tuyere arrangement.Described dropping tuyere arrangement has a nozzle with minor diameter.The stock liquid that transfer is come drips the aqueous solution of ammonia into from the end of nozzle.The uranyl nitrate (described drop has been dropped in the aqueous solution of ammonia) that is included in the drop changes ammonium diuranate from the surface of drop into by reaction.Stop the time that is enough to finish reaction in this solution if contain the drop of uranyl nitrate, the uranyl nitrate of each drop centered part is all changed into ammonium diuranate so.
Falling in the process on ammonia soln surface, the drop that drips from nozzle passes through ammonia atmosphere.This ammonia produces gelification on the surface of each drop, and this has formed film on the drop surface.Drop with described film prevents distortion to a certain extent, and described distortion is that the impact of generation when drop is fallen and clashed into ammonia soln surperficial causes.Fully react if be included in the uranyl nitrate and the ammonia of the drop that falls into solution, so just will form the ammonium diuranate particle, described ammonium diuranate particle can be abbreviated as " ADU particle " sometimes.
So the ADU particle that forms is washed, and drying is calcined in atmosphere then, and this changes into the uranium trioxide particle with the ADU particle.The uranium trioxide particle that obtains is reduced and sintering, is converted to by these step 3 uranium oxide particles to have highdensity uranium dioxide particle, and described uranium dioxide particle is in the state of similar pottery.Described uranium dioxide particle is sieved, or classification, obtains the fuel kernel particle of diameter within pre-determined range.
When after forming coat on the nuclear particle, the fuel fabrication that will be used for the high-temperature gas reactor becomes fuel compact or fuel sphere.Described fuel compact or ball obtain in the following way: described fuel and the graphite-based material of being made by powdered graphite, tackiness agent and other component are compressed or molded cylinder, hollow cylinder or the spheroid with content that become, and compression or molded product are calcined.Referring to The Nikkan Kogyo Shimbun, Ltd. " the Genshiro Zairyo Handbook " that publishes on October 31st, 1977, or " A handbook about Nuclear ReactorMaterials ", and Ohmsha, " GenshiryokuHandbook " or " Nuclear Energy Handbook " that Ltd. published in December 20 nineteen ninety-five.
The manufacturing of describing in " Genshiro Zairyo Handbook " is used for the method for high-temperature gas reactor fuel, and stock liquid (from its preparation ammonium diuranate particle) is to prepare by pure water and thickening material are added the uranyl nitrate reserve liquid and stir resulting mixture.But this reference book lacks preparing the explanation of required detailed conditions.If the technician in nuclear energy field only reads this this book, can not make the ammonium diuranate particle that has good sphericity and have the zero defect internal structure.
By making for example uranous uranic oxide reaction of nitric acid and uranium oxide, according to following reaction formula, the preparation uranyl nitrate:
Based on reaction formula (1), experienced technician can expect, when using 2.66mol or more nitric acid for 1mol uranium, can prepare uranyl nitrate in stoichiometry ground, can not be left for example uranous uranic oxide of unreacted uranium oxide.But, using that nitrogen content is raised inevitably in the very high and waste fluid of the ordinary method cost of excessive nitric acid, this causes environmental pressure to increase the weight of.On the other hand, when use is less than 2.66mol nitric acid for 1mol uranium, will for example unreacted uranous uranic oxide of the stoichiometry ground unreacted uranium oxide of residue after reaction.Unreacted uranium oxide is included in the uranyl nitrate reserve liquid sometimes, and this causes and can not make the ammonium diuranate particle by plan in advance.In addition, experienced technician will can not reckon with and can make the ammonium diuranate particle with good sphericity.
Disclosure of the Invention
[problem that the present invention will solve]
The objective of the invention is to overcome the problem relevant with routine techniques.
A target of the present invention provides the method that preparation is used to make ammonium diuranate particulate stock liquid, wherein said ammonium diuranate particle has good sphericity and flawless internal structure, makes the fuel kernel with good sphericity with high yield from described ammonium diuranate particle.
Another target of the present invention provides the method for preparing uranyl nitrate solution with low cost, described method can be in uranium oxide and nitric acid (its quantity is lowered with respect to the quantity of uranium) reaction, and manufacturing has the ammonium diuranate particle of good quality and reduces environmental pressure.
[method of dealing with problems]
First mode of dealing with problems is to be 4.0 * 10 15 ℃ of following viscosity
-2-6.5 * 10
-2The stock liquid of Pas is used to make the ammonium diuranate particle.
Second mode is the stock liquid according to first mode, and wherein this stock liquid comprises uranyl nitrate, tetrahydrofurfuryl alcohol and polyvinyl alcohol.
Third Way is the method that preparation is used to make ammonium diuranate particulate stock liquid, described method comprises that mixed nitrate uranyl solution and tetrahydrofurfuryl alcohol are to make the uranyl nitrate mixture, with the water-soluble preparation polyvinyl alcohol water solution of polyvinyl alcohol, polyvinyl alcohol water solution is mixed with tetrahydrofurfuryl alcohol to prepare polyvinyl alcohol solution and the uranyl nitrate mixture is mixed with polyvinyl alcohol solution.
Cubic formula is the method according to Third Way, and wherein based on the cumulative volume of stock liquid, the total quantity of polyvinyl alcohol water solution is 15-20 volume % in stock liquid.
The 5th mode is the method according to Third Way or cubic formula, and wherein based on the cumulative volume of stock liquid, the total quantity of tetrahydrofurfuryl alcohol is 40-50 volume % in stock liquid.
The 6th mode is that wherein the uranyl nitrate mixture is under agitation to carry out with mixing of polyvinyl alcohol solution according to each method of first to the 5th mode, is thereafter the degassing and by adding the pure water adjusted volume.
The 7th mode is that wherein the uranium content in the stock liquid is 0.6-0.9mol-U/L according to each method of the 3rd to the 6th mode.
The from all directions formula be according to each method of the 3rd to the 7th mode, wherein when prepare polyvinyl alcohol solution by mix polyethylene alcohol solution and tetrahydrofurfuryl alcohol, to be that the temperature at polyvinyl alcohol water solution is minimum be reduced to adding before 50 ℃ to tetrahydrofurfuryl alcohol.
The 9th mode is the method that preparation is used to make ammonium diuranate particulate stock liquid, and described stock liquid comprises uranyl nitrate, polyvinyl alcohol water solution and tetrahydrofurfuryl alcohol, and wherein polyvinyl alcohol is to carry out weighing when it is under the drying regime.
The tenth mode is the method according to the 9th mode, and wherein said dry polyethylene alcohol is the polyvinyl alcohol preparation that is absorbed with moisture by heating.
The 11 mode is according to the method for the 9th mode, and wherein said dry polyethylene alcohol is the polyvinyl alcohol that stores with siccative.
The 12 mode is the method for preparing uranyl nitrate solution, wherein this uranyl nitrate solution is used for manufacturing and is used to prepare ammonium diuranate particulate stock liquid, thereby described method comprises that making nitric acid and uranium oxide reaction make the nitric acid (A) and the mol ratio (A/B) of uranium (B) is 2.1-2.6.
The 13 mode is the method according to the 12 mode, and wherein 70-110 ℃ the temperature of being reflected between nitric acid and the uranium oxide is carried out.
The tenth cubic formula is the method according to the 12 or 13 modes, further comprises the step of the NOx gas that wherein chemical treatment produces in reaction.
The 15 mode is the method that preparation is used for polyvinyl alcohol solution, wherein said polyvinyl alcohol solution is used for manufacturing and is used to prepare ammonium diuranate particulate stock liquid, described method comprises that the pure and mild water of mix polyethylene mixes with tetrahydrofurfuryl alcohol with the polyvinyl alcohol water solution of preparation 6-9 quality % with this polyvinyl alcohol water solution.
The 16 mode is the method according to the 15 mode, wherein is heated under 75 ℃ the situation of temperature polyvinyl alcohol is soluble in water at least at the polyethylene alcohol and water.
The 17 mode is the method according to the 15 or 16 modes, wherein based on the cumulative volume of the tetrahydrofurfuryl alcohol that contains in the stock liquid, the tetrahydrofurfuryl alcohol of 1-50 volume % is mixed at least 50 ℃ temperature with polyvinyl alcohol water solution.
The present invention uses a kind of stock liquid, and its viscosity is adjusted to 4.0 * 10
-2-6.5 * 10
-2Pas, this can make from the drippage nozzle and keep their sphere that is shaped as to the drop that ammonia soln falls by surface tension, and this prevents drop because the impact of generation and break easily or be out of shape when drop is fallen and clashed into ammonia soln surperficial.And the viscosity in this scope prevents that stock liquid from clogging in nozzle, wherein drops out by described nozzle droplets of feed.Therefore, the stock liquid that contains uranyl nitrate that drippage has a particular viscosity makes can make the ammonium diuranate particle with good sphericity, and this causes making the fuel kernel with good quality.
The invention provides a kind of stock liquid, this stock liquid has such viscosity, promptly when raw material from the drippage nozzle when ammonia soln drips, the drop of drippage keeps their sphere that is shaped as by surface tension, this prevents drop because the impact that takes place when drop is fallen and clashed into ammonia soln surperficial and break easily or be out of shape, and it provides by utilizing following mode to prepare stock liquid: mixed nitrate uranyl solution and tetrahydrofurfuryl alcohol (it may be called " THFA " sometimes later on) are to prepare the uranyl nitrate mixture; Mix polyethylene alcohol solution (may be called " PVA aqueous solution " after it sometimes, its by with soluble in water the making of polyvinyl alcohol (it may be called " PVA " later)) and THFA are with preparation polyvinyl alcohol solution (it may be called " PVA solution " sometimes); With mixed nitrate uranyl mixture and PVA solution.Have good sphericity from the ammonium diuranate particle of prepared according to the methods of the invention stock liquid manufacturing, and make fuel kernel with good sphericity from this ammonium diuranate with good sphericity.
In the method for manufacturing stock liquid according to the present invention,, this means the PVA of measuring predetermined weight exactly will when PVA is under the drying regime, weighing with the PVA in the uranyl nitrate mixture blended PVA solution.So this drying-Weighing method prevents to prepare owing to weighing and adding wet thickening material and causes viscosity to be lower than the stock liquid of predetermined viscosity.The drop of being made by the stock liquid of the inventive method that falls from the drippage nozzle can keep spherical form.Even be subjected to the impact to them when the droplet impact ammonia soln, drop also can keep their shape and the gained ammonium diuranate particle that forms in ammonia soln is difficult to distortion.Therefore, can prepare the ammonium diuranate particle with good sphericity, this causes having with the high yield manufacturing fuel kernel of good sphericity.
The method of manufacturing uranyl nitrate solution of the present invention uses the nitric acid of 2.1-2.6 to uranium (nitric acid/uranium) mol ratio, and it prevents to occur undissolved resistates when for example uranous uranic oxide is dissolved in the nitric acid when uranium oxide.This specific molar ratio range also increased uranous uranic oxide in nitric acid solubleness and reduced the quantity of the nitric acid that is used for this reaction.Therefore, compare with ordinary method, the total quantity of waste liquid can be lowered, and this transfers to have reduced again the preparation cost of uranyl nitrate solution.In addition, because the uranyl nitrate of preparation does not comprise undissolved resistates, so the droplets of feed with predetermined uranium content can be added in the ammonia soln in each batch, this causes forming the ammonium diuranate particle that has good sphericity and have the zero defect internal structure.And, when dry mixed has the uranium powder of two or more degree of enrichment, can make ammonium diuranate particle, because prepared uranyl nitrate solution does not comprise undissolved resistates with predetermined degree of enrichment.Can make fuel kernel from ammonium diuranate particle with good sphericity and zero defect internal structure with good sphericity and zero defect internal structure.
In addition, the reduction of the nitric acid quantity of use is accompanied by the reduction of nitrogen quantity in the waste liquid.And, can reduce the quantity of the ammonium nitrate that forms by the reaction between ammonia soln and the nitric acid, this so that reduced the quantity of the ammonium nitrate that adheres to the ammonium diuranate particle surface again.Then, can reduce the quantity that is used for warm water that the ammonium nitrate that adheres to the ammonium diuranate particle surface is washed off.Therefore, can reduce the burden that nitrogen in the waste fluid and useless warm water cause environment.
The method of the PVA of preparation solution of the present invention can provide the PVA aqueous solution that is suitable for making stock liquid, and this stock liquid comprises uranyl nitrate and do not comprise undissolved PVA resistates, and this stock liquid has predetermined viscosity.
Because PVA is soluble in water at least 75 ℃ temperature, so the dissolving of PVA in water carried out rapidly and do not had a undissolved solid PVA resistates.
In the present invention, the THFA and the PVA aqueous solution that are included in the predetermined portion of the THFA total quantity in the stock liquid mix in predetermined temperature, this causes making the stock liquid with predetermined viscosity, can prepare the ammonium diuranate particle with good sphericity and the deterioration that has the zero defect internal structure and do not have to cause owing to gelification from this stock liquid.
The accompanying drawing summary
Fig. 1 is the schema that expression prepares the method for stock liquid of the present invention.
Fig. 2 is the figure that shows the equipment example be used to prepare uranyl nitrate solution.
Fig. 3 is the optical microscope photograph that is presented at an ammonium diuranate particulate part that obtains among the work embodiment 1.
Fig. 4 is the synoptic diagram that shows the method for measuring the fuel kernel sphericity.
Fig. 5 shows the figure that concerns between stock liquid viscosity and the fuel kernel productive rate.
Fig. 6 is the optical microscope photograph that is presented at an ammonium diuranate particulate part that obtains among the comparative example 2.
[Reference numeral explanation]
Reference numeral 1 expression reaction vessel, the 2nd, the nitric acid storage tank, the 3rd, uranium oxide is introduced hopper, and the 4th, well heater, the 5th, the device and 6 of handling NOx is whipping apptss.
Preferred forms of the present invention
(1) stock liquid
Stock liquid of the present invention is a kind of liquid that contains uranyl nitrate, and it is applicable to the fuel kernel of making the high-temperature gas reactor.Stock liquid of the present invention has 4.0 * 10
-2-6.5 * 10
-2The viscosity of Pas, this scope is corresponding to 40-65cP.When the viscosity of stock liquid is in this scope, can make ammonium diuranate particle with good sphericity.On the other hand, if the ammonium diuranate particle that viscosity less than this scope, obtains tends to have poor shape, maybe can not make ammonium diuranate particle with good sphericity.If viscosity surpasses the upper limit, the viscosity of stock liquid may be excessive and cause the drippage nozzle can not normally drip stock liquid, because nozzle is blocked.In addition, such high viscosity may cause being formed on the ammonium diuranate particle that has defective in the internal structure.
Have the stock liquid that is in the viscosity in the described scope and can comprise a kind of solution, this solution comprises uranyl nitrate, tetrahydrofurfuryl alcohol and polyvinyl alcohol.
As substituting of tetrahydrofurfuryl alcohol, can use water-soluble cyclic ether, for example trimethylene oxide, tetrahydrofuran (THF) and dioxane with 1-4 carbon atom; With water-soluble cyclic ether with alkanol groups, be bonded to above-mentioned water-soluble cyclic ether by the alkanol groups that will have 1-3 carbon atom and obtain, for example 2, the 5-tetrahydrofurandimethanol.
As substituting of polyvinyl alcohol, can use synthetic polymer for example sodium polyacrylate and polyethylene oxide; Cellulose polymer compound is carboxymethyl cellulose, Natvosol, methylcellulose gum and ethyl cellulose for example; Starch polymer is Zulkovsky starch and carboxymethyl starch for example; With water-soluble natural polymkeric substance for example dextrin and Polygalactan.
The quantity of uranyl nitrate 0.6-0.9mol-U/L typically in the stock liquid.When the quantity of uranyl nitrate is in this scope, the uranium dioxide fuel nuclear that preparation has good sphericity under the situation of well reproduced can be had.When described quantity is not in this scope, may produce the uranium dioxide fuel nuclear of sphericity difference.
The quantity of THFA preferably 40-50 volume %, more preferably 43-47 volume % in whole stock liquid.When the quantity of THFA is in this scope, the uranium dioxide fuel nuclear that preparation has good sphericity under the situation of well reproduced can be had.When described quantity is not in this scope, may produce the uranium dioxide fuel nuclear of sphericity difference.
The quantity of PVA typically should be 10-15g/L in the stock liquid.PVA quantity in this scope makes and the viscosity of stock liquid can be remained in the favourable scope that this causes having with the manufacturing of ideal reproducibility the uranium dioxide fuel nuclear of good sphericity.The quantity that is less than 10g/L may cause producing the uranium dioxide fuel nuclear of sphericity difference.On the other hand, if this quantity surpasses 15g/L, may be created in the uranium dioxide fuel nuclear that has defective in the internal structure.
Stock liquid of the present invention may further include other component, does not realize target of the present invention as long as these components do not hinder.The example of described other component can be thickening material and stablizer.
(2) prepare the method for stock liquid
As shown in fig. 1, the basic step for preparing the method for stock liquid of the present invention comprises: uranyl nitrate solution is mixed with THFA with preparation uranyl nitrate mixture, PVA is soluble in water with the preparation PVA aqueous solution, mix the described PVA aqueous solution and THFA to prepare PVA solution and to mix described uranyl nitrate mixture and described PVA solution.
(2-1) preparation uranyl nitrate solution
Uranyl nitrate solution can be by the method preparation for preparing uranyl nitrate solution of the present invention.
In the preparation method, nitric acid (A) is to the mol ratio of uranium (B) (both participates in the reaction), being A/B, is very important, and this value is by obtaining the mole number of the used nitric acid mole number divided by the uranium that is comprised in the uranium oxide (for example uranous uranic oxide) that uses in the reaction.
Uranyl nitrate solution can by make nitric acid and uranium oxide for example uranous uranic oxide react according to following reaction formula and obtain:
Nitric acid and uranium oxide for example the possible reaction of another between the uranous uranic oxide shown in following reaction formula.
Therefore, mol ratio should be 2.1-2.6, particularly 2.3-2.5.
When mol ratio less than 2.1 the time, exist such possibility be uranium oxide for example uranous uranic oxide may not exclusively be dissolved in the nitric acid, may have the uranium oxide resistates.On the other hand, if mol ratio surpasses 2.6, the nitric acid quantity that is used for reacting increases, and this transfers to increase again the manufacturing cost of uranyl nitrate solution.In addition, the nitrogen quantity that is derived from nitric acid in the waste fluid increases, and this may cause burden to environment.
The present invention uses aqueous nitric acid, and its concentration is 50 quality % or bigger typically, preferred 60 quality % or bigger.
Though uranium oxide for example uranous uranic oxide can be particle or form of powder, however the uranium oxide of powder type preferably, and it is easy to be dissolved in the nitric acid fast and fully.
In the preferred embodiment of present method, 70-110 ℃ temperature, nitric acid and uranium oxide for example uranous uranic oxide react.
If temperature is lower than 70 ℃, uranium oxide may not can fully dissolves and may not make the uranyl nitrate solution of uranium content in above-mentioned scope.
For the uranium oxide among the present invention, can use uranous uranic oxide suitably.But, can use the uranium oxide except that uranous uranic oxide, for example uranium dioxide or uranium trioxide.
The method for preparing uranyl nitrate solution should further comprise the step that is used for the NOx gas that produces between the chemical treatment reaction period.
The method of handling NOx in this step can be the wherein wet method of absorption of N Ox gas and the dry method of reducing NOx gas in the presence of catalyzer wherein in alkali.
The example of described alkali comprises sodium hydroxide, yellow soda ash, magnesium hydroxide, calcium hydroxide and ammonia.Described catalyzer can comprise three-way catalyst.
The example that is used for preparing the equipment of uranyl nitrate solution of the present invention is shown in Fig. 2.
In Fig. 2, alphabetical Reference numeral A represents to be used to prepare the equipment of uranyl nitrate solution, digital Reference numeral 1 expression reaction vessel, and the 2nd, the nitric acid storage tank, the 3rd, uranium oxide is introduced hopper, and the 4th, well heater, the 5th, the device and 6 of handling NOx gas is whipping apptss.
Reaction vessel 1 be wherein uranium oxide for example thereby uranous uranic oxide and nitric acid react the container of preparation uranyl nitrate solution.
Though reaction vessel 1 there is not particular restriction, preferably corrosion-resistant, heat-resisting and withstand voltage and can be by the container of tight seal.
The material of reaction vessel 1 can comprise aluminium alloy, magnesium alloy, titanium alloy and stainless steel.
To the size and dimension of this reaction vessel without limits.But, when the shape and size by the control container guarantee criticality safety, just form reaction vessel to satisfy required shape and size as requested.
Nitric acid storage tank 2 is the jars that wherein store nitric acid.Described jar is connected to reaction vessel 1 by pipeline and pump P2.
To the material of nitric acid storage tank 2, size and dimension without limits.
The nitric acid that is stored in the nitric acid storage tank 2 is transported in the reaction vessel 1 by pump P2.Described transporting can be carried out continuously or off and on.
Uranium oxide is introduced hopper 3 and is accommodated for example uranous uranic oxide of uranium oxide.Hopper 3 is connected to reaction vessel 1 by feeder, and this feeder does not illustrate in the drawings.
Material, the size and dimension of uranium oxide being introduced hopper 3 do not have particular restriction.
Be stored in uranium oxide introduce in the hopper 3 uranium oxide for example uranous uranic oxide be introduced in the reaction vessel 1 by described feeder.
For described feeder, can use any known feeder, its example is rotary feeder or dull and stereotyped feeder.
Well heater 4 is the devices that are used to heat uranyl nitrate solution.
For well heater 4, can use any known heating unit, as long as it can be heated to uranyl nitrate solution suitable temperature.This well heater comprises the heating unit of type of heating such as utilizing electricity, hot water, microwave exposure.
The device 5 of handling NOx gas is that the by product NOx gas processing that is used for reaction is the device of non-toxic substance.This device is connected to reaction vessel 1 by pipeline and pump P1.
The special extra demand that does not have described device to satisfy, the concentration that needs only NOx gas in the emission gases that obtains by processing NOx gas is lower than environmental standard.
Whipping appts 6 there is not particular restriction.The example of whipping appts 6 is revolving stirrer and middling speed revolving stirrer at a slow speed.
The speed of rotation of the rotor of whipping appts 6 should be 100-300rpm.Rotation can be successive or intermittence.
By being used to prepare the device A of uranyl nitrate solution, for example can prepare uranyl nitrate solution as follows.
At first, from uranium oxide introduce hopper 3 with the uranium oxide of pre-determined quantity for example the uranous uranic oxide powder send into the reaction vessel 1.
Then, after NOx gas treatment equipment 5 starts, the nitric acid of pre-determined quantity is transported to reaction vessel from nitric acid storage tank 2.
After this, start whipping appts 6 and well heater 4.
Reaction mixture in the reaction vessel 1 is maintained at predetermined steady temperature and reacts preset time.
Behind reaction terminating,, solution just can be obtained uranyl nitrate solution from reaction vessel 1 taking-up by known discharge method.
(2-2) preparation of uranyl nitrate mixture
Be mixed with the uranyl nitrate mixture by the uranyl nitrate solution and the THFA that will so make.
The total quantity of THFA 40-50 volume % typically in whole stock liquid, preferred 43-47 volume %.When the total quantity of THFA in the stock liquid was in the described scope, the content of the uranyl nitrate in the drop that is formed by stock liquid can be not too small, and make the modest viscosity of stock liquid.Quantity in described scope makes and can form that to cause final product be the drop that fuel kernel has good sphericity.Calm miscible viewpoint sees, the THFA quantity that is used to prepare this uranyl nitrate mixture should be 50-99 volume %.
The mixing of uranyl nitrate and THFA should be cooled to 15 ℃ or more carry out during low temperature at mixture.Described married operation preferably carries out in the storage tank of preparation stock liquid.If the mixing of uranyl nitrate and THFA can be maintained at about 15 ℃ or more carry out under the situation of low temperature at mixture, so described storage tank can be any storage tank.
(2-3) preparation of the PVA aqueous solution
Can be by preferably obtaining the PVA aqueous solution at Heating temperature mixing PVA and water in room temperature.
In the present invention, preferably use dry PVA.The reason of using dry PVA is that the accurate weighing of PVA makes and can the preparation of reproducibility ground will be used for making suitably ammonium diuranate particulate stock liquid, the uranium dioxide particle that can have good sphericity from described ammonium diuranate particle with the good yield manufacturing.
The PVA that absorbs moisture by thorough drying obtains exsiccant PVA.Wet PVA can be dried to the degree that for example can realize in the following way: the PVA that will wet puts into the moisture eliminator that comprises siccative and the device inside that keeps dry is in that the weight up to PVA no longer reduces under the high vacuum.For example dry PVA obtains in the following way: the PVA that will wet puts into drying machine, for example wherein has the moisture eliminator of siccative, and the inside of the machine that keeps dry is under the high vacuum a whole day at least.Method for dry PVA, except will wet as mentioned above PVA and siccative remain under normal pressure or the high vacuum, can use to be included in PVA that normal pressure or decompression down add thermal absorption moisture to the pyritous heating and drying method, or the freeze-drying method that is included in repeated freezing under the high vacuum and wet PVA is defrosted.So exsiccant PVA should remain under the drying conditions, thereby described PVA can not absorb moisture before being used to method of the present invention.
In described heating and drying method or freeze-drying method, the temperature of handling comprises that Heating temperature and described processing comprise the heating and continuous time cycle, be not all the same in all cases, but difference according to circumstances depend on conditions such as for example processed PVA quantity and heating means.When the weight of processed PVA stopped to reduce, operator should judge and obtained exsiccant PVA.Certainly, can not use PVA will be out of shape, take place the heating condition of change of properties or decomposition.Typically, Heating temperature is that 70-90 ℃ and heat-up time approximately are 20 minutes to 2 hours.
For the thermal treatment of the PVA that absorbs moisture, needn't use special heating unit.But the example that can be used for this type of device of the present invention is wherein to place and heat process furnace or the pipe of wet PVA and place wet PVA and with the plate or the basket of warm air blowing.
When utilizing the PVA that is dried by for some time that PVA and siccative are kept together, for example gac, active aluminum or silica gel for example store certain hour in the moisture eliminator at container with siccative the PVA that has been dried.For siccative, silica gel preferably.Cycle in storage time difference according to circumstances depends on for example with PVA weight and its quantity of being stored.When the decline of PVA weight stopped, operator should judge that he has obtained exsiccant PVA.Generally speaking, that be fit in the present invention use is exsiccant PVA, and it is to obtain by heating or with the dry PVA that absorbs moisture of siccative.
The quantity of PVA typically should be 10-15g/L in the stock liquid.When quantity was in this scope, the viscosity of stock liquid can be maintained at favourable condition and can make the ammonium diuranate particle with good sphericity in reproducibility ground.When quantity is not in this scope, may produce the ammonium diuranate particle of sphericity difference.
The quantity of PVA in the PVA aqueous solution is 6-9 quality % typically, preferred 7-8 quality %.When the quantity of the PVA in the PVA aqueous solution was in this scope, the viscosity that contains the stock liquid of uranyl nitrate can advantageously be maintained at 4.0 * 10 at 15 ℃
-26.5 * 10
-2Pas.In addition, this scope can not cause undissolved PVA to remain in the PVA aqueous solution.
When the quantity of the PVA in the PVA aqueous solution during less than 6 quality %, the stock liquid viscosity that obtains is too little, and this makes stock liquid suitably not drip.On the other hand, the PVA content above 9 quality % causes undissolved PVA to remain in its aqueous solution.
Heating temperature, or the heated temperature of the mixture of PVA and water should be 75 ℃ at least.75 ℃ or higher Heating temperature make and can prepare the even PVA aqueous solution that does not have undissolved PVA resistates.
The mixing of PVA and water is undertaken by stirring usually.Normally 80-100 minute stirring cycle.When heated when simultaneously mixture being stirred, because evaporation of water, the water-content of mixture may descend.By suitably adding the quantity that water comes the water of compensate for evaporation to heated mixture.
(2-4) preparation of PVA solution
Then, prepare PVA solution by mixing the PVA aqueous solution and THFA,
Relation between the quantity of the PVA aqueous solution and the quantity of THFA is such: the quantity of the PVA aqueous solution accounts for whole stock liquid 15-20 volume %, and based on the total quantity of THFA in the stock liquid, the quantity of THFA is 1-50 volume %, particularly 30-40 volume %.
When the quantity of THFA is in the described scope, can obtain the wherein homodisperse PVA solution of PVA.
In addition, when THFA and PVA aqueous solution, THFA is should be in the temperature of the PVA aqueous solution minimum to add before being reduced to 50 ℃ preferred 60 ℃.
If after the temperature of solution is cooled to be lower than 50 ℃ THFA is joined the PVA aqueous solution, the PVA in the PVA solution may be frozen into gel, and this may cause some troubles when dripping stock liquid.
(2-5) mixing of uranyl nitrate mixture and PVA solution
By mixed nitrate uranyl mixture and PVA formulations prepared from solutions stock liquid.
Under agitation mixed nitrate uranyl mixture and PVA solution outgas and then by adding the pure water adjusted volume.This step makes that the content of uranium is identical in each batch stock liquid.Therefore, the ammonium diuranate particle that obtains having good sphericity He have the zero defect internal structure, wherein each described particle contains the uranium of identical weight.
After its volume and the adjustment of viscosity process, the uranium content of stock liquid should be 0.6-0.9mol-U/L.
When the uranium content of stock liquid after its volume adjustment during less than 0.6mol-U/L, relatively the quantity of PVA increases, and this means that the viscosity of stock liquid is too big.The result is, dripping nozzle may be blocked, and this has stoped the dropping of stock liquid, and may be created in the ammonium diuranate particle that has defective in its internal structure.
On the other hand, when the uranium content of stock liquid after its volume adjustment was higher than 0.9mol-U/L, relatively the quantity of PVA reduced, and this means that the viscosity of stock liquid is lowered.The viscosity that is lowered may influence the quality of fuel kernel, for example its sphericity unfriendly.
(3) be used for the preparation of the fuel of high-temperature gas reactor
So the stock liquid of preparation is cooled to predetermined temperature and adjusts its viscosity.Then, stock liquid is added dropwise to ammonia soln from the dropping nozzle with minor diameter.
The process that the surface towards ammonia soln falls, pass through ammonia atmosphere from the drop of nozzle drippage.This ammonia produces gelification on the surface of each drop, this has alleviated by the distortion of falling when drop and drop receives when clashing into ammonia soln surperficial that impact caused.The uranyl nitrate and the ammonia that are included in the drop that falls into solution fully react, and drop is converted to the ammonium diuranate particle, and described ammonium diuranate particle may be abbreviated as " ADU particle " sometimes.
So the ADU particle that forms is washed, and drying is calcined in atmosphere then, and this changes into the uranium trioxide particle with the ADU particle.The uranium trioxide particle that obtains is reduced and sintering, is converted to by these step 3 uranium oxide particles to have highdensity uranium dioxide particle, and described uranium dioxide particle is in the state of similar pottery.Described uranium dioxide particle is sieved, or classification, obtains the fuel kernel particle of diameter within pre-determined range.
The structure of the fuel pellet that is used for the high-temperature gas reactor by using described fuel kernel manufacturing is above describing.
The fuel fabrication that will be used for the high-temperature gas reactor becomes fuel compact or fuel sphere.Described fuel compact or ball obtain in the following way: described fuel and the graphite-based material of being made by powdered graphite, tackiness agent and other component are suppressed or molded cylinder, hollow cylinder or the spheroid with content that become, and compacting or molded product are calcined.
Embodiment
By work and the comparative example present invention is described.Certainly, the present invention has more than and is limited to described work embodiment, but can suitably change in main idea scope of the present invention.
(work embodiment 1)
In aforesaid embodiment, prepare stock liquid under the described below condition.When preparation is 5.2 * 10 15 ℃ of viscosity
-2During the stock liquid of Pas (corresponding to 52cP), use following condition.
The quantity of THFA in the whole stock liquid: 45 volume %
The quantity of the PVA aqueous solution in the whole stock liquid: 18 volume %
The PVA required time soluble in water: 90 minutes
The concentration of the PVA aqueous solution: 7.3 quality %
Based on the total quantity of the THFA that contains in the stock liquid, be included in the quantity of the THFA in the PVA solution: 37 volume %
The content of uranium: 0.76mol/L in the stock liquid after regulating the stock liquid volume
The mole number of nitric acid is to the ratio of uranium mole number after regulating the stock liquid volume: 2.3
Prepared stock liquid with different viscosity by the change condition.Then, prepared fuel kernel according to previously described method.The viscosity of stock liquid uses the vibration viscosity apparatus that is called " Viscomate VM-1A-L " to measure, and this viscosity apparatus is by Yamaichi Electronics Co., and Ltd makes.
[evaluation method and result]
Internal structure from the ammonium diuranate particle (or ADU particle) made by the stock liquid for preparing the embodiment is estimated.
So the ADU particle that forms is dried and calcines in atmosphere then, and this changes into the uranium trioxide particle with the ADU particle.The uranium trioxide particle that obtains is reduced and sintering.Be converted to and have highdensity uranium dioxide particle by reduction and sintering step uranium trioxide particle, be in the state of similar pottery.Described uranium dioxide particle is sieved, or classification, obtains the fuel kernel particle (or uranium dioxide particle) of diameter within pre-determined range.Sphericity to the fuel kernel (or uranium dioxide particle) that obtains is estimated.And, calculated from the productive rate of the fuel kernel of different viscosity stock liquids manufacturings.
[evaluation method of ADU granule interior structure]
With the ADU particle polishing that obtains, and with its various piece of observation by light microscope, thereby determine whether to exist for example fissured defective.Observation to various piece confirms to have formed the particle with even internal structure.Referring to Fig. 3.
[estimating the method for fuel kernel sphericity]
Measure the sphericity value of fuel kernel (or uranium dioxide particle) by the PSA method.As shown in Figure 4, the PSA method is a kind of method of using photorectifier, slit and light source.Light beam from light source arrives fuel kernel (or uranium dioxide particle) by slit, detects the shade of the following junk that moves between photorectifier and slit with photorectifier.The shade that detects from photorectifier obtains particle size.Repeat above-mentioned steps, detect the shade of fuel kernel from a plurality of directions.From the particle size that derives from described shade can computing fuel nuclear (or uranium dioxide particle) sphericity.
By this PSA method, uranium dioxide particle sizing 50 times, sphericity is defined as the ratio of maximum particle size to the smallest particles size.Measure 100 uranium dioxide particles and calculate its sphericity value.For example when 95% or more particles have 1.2 or during littler sphericity, can think that described particle has good sphericity on the whole.
[evaluation of fuel kernel productive rate]
Estimate productive rate according to following equation.Evaluation result is shown among Fig. 5.
Wa/Wb×100(％)
Wa: the weight (g) of the uranium by particle size selection check as described below and sphericity selection check.
Wb: the weight of participating in the uranium of check.
The fuel kernel particle that obtains is implemented particle size selection and sphericity selection.Particle size is selected to implement as follows: use several sieves with different sieve apertures to filter out the fuel kernel particle and select the fuel kernel particle of particle size in pre-determined range.Sphericity is selected to implement as follows: provide the fuel kernel particle to the plate of slight inclination and vibration and select straight line to tumble the fuel kernel of described plate.
Show to the evaluation of ammonium diuranate particle (or ADU particle) internal structure and to the evaluation of fuel kernel sphericity and to have obtained good ammonium diuranate particle (or ADU particle) and fuel kernel.In addition, the diagram from Fig. 5 is appreciated that at 15 ℃ and has about 4.0 * 10
-26.5 * 10
-2The stock liquid of the viscosity between the Pas (it is corresponding to 40-65cP) provides good productive rate.Described digital proof stock liquid of the present invention can provide the fuel kernel with better quality.
(work embodiment 2)
By being joined, 300g powdery polyethylene alcohol (or PVA powder) obtains a kind of liquid mixture in the 4L pure water.This mixture was stirred 90 minutes at 95 ℃, and this has produced a kind of PVA aqueous solution, and its PVA content is 7 quality %.In the aqueous solution of so preparation, do not observe undissolved PVA resistates.Then, in this PVA aqueous solution, add 4L tetrahydrofurfuryl alcohol (or THFA), obtain PVA solution at 80 ℃.
With the PVA solution that so makes, mix with uranyl nitrate mixture and the pure water that the THFA of about 7L prepares by mixing about 9L uranyl nitrate solution, thereby preparation contains the stock liquid of uranyl nitrate.
Measure the viscosity of the stock liquid of preparation in work embodiment 2 with viscosity apparatus (Yamaichi Electronics Co., the product of Ltd).Viscosity is 5.5 * 10 at 12 ℃
-2Pas, it is corresponding to being 5.0 * 10 at 15 ℃
-2Pas.
By being added, droplets of feed prepared the ammonium diuranate particle in the ammonia soln.After drying,, and observe various piece along the described particle of the plane cutting that comprises each particle diameter.Observe each particle of proof and all have uniform internal structure.Estimate the sphericity value of fuel kernel according to the method for above-mentioned evaluation fuel kernel sphericity.The result is that the percentage ratio of defective fuel kernel is no more than 1%.
(comparative example 1)
Prepare stock liquid according to the step of work among the embodiment 2, except the quantity of PVA is 230g, this means that using PVA content is the PVA aqueous solution of 5.4 quality %.
Use identical viscosity apparatus to measure the viscosity of the stock liquid that in this comparative example, prepares.The result is that viscosity is 3.5 * 10 at 15 ℃
-2Pas, this viscosity is lower than the viscosity of the stock liquid of preparation in work embodiment 2.
Be dried from the ammonium diuranate particle of described stock liquid preparation, and calcine in atmosphere, this changes into the uranium trioxide particle with the ADU particle.The uranium trioxide particle that obtains is reduced and sintering.Be converted to and have highdensity uranium dioxide particle by reduction and sintering step uranium trioxide particle, described uranium dioxide particle is in the state of similar pottery.Described uranium dioxide particle is sieved, or classification, obtains fuel kernel or the uranium dioxide particle of particle size within pre-determined range.
Resulting fuel kernel (or uranium dioxide particle) carries out the sphericity evaluation according to aforesaid method, and removes the fuel kernel (or uranium dioxide particle) with defective sphericity.Abandoned 7% fuel kernel.
Can think that thus this result is that the low viscosity by stock liquid causes; Low viscosity has reduced from the surface tension of each drop that drips the nozzle drippage, and this makes each drop be difficult to keep it to form sphere and causes corresponding ammonium diuranate particulate distortion.
(comparative example 2)
Prepare stock liquid according to the step of work among the embodiment 2, except the quantity of PVA is 400g, this means that using PVA content is the PVA aqueous solution of 9.1 quality %.
In the PVA aqueous solution of this comparative example's preparation, observe resistates, do not obtained the wherein even PVA aqueous solution of the perfect dissolved of PVA.Prepared the ammonium diuranate particle by dripping described stock liquid to ammonia soln.After drying,, and observe various piece along the described particle of the plane cutting that comprises each particle diameter.Observe each particle of proof and have the internal structure that has defective.Referring to Fig. 6.Can think that thus this result is by due to the following fact: the PVA content of stock liquid is excessive to make the reaction between ammonia and the uranyl nitrate can not be advanced to the centre portions of each drop.
(work embodiment 3)
Powdered uranium oxide is joined in the nitric acid and mixture was stirred 1.5 hours at 100 ℃.Thereby having prepared uranium content is the uranyl nitrate solution of 2.4mol-U/L.In this uranyl nitrate solution, add the 4L tetrahydrofurfuryl alcohol and mix the mixture that obtains.Obtain the uranyl nitrate mixture.On the other hand, tetrahydrofurfuryl alcohol is added in the polyvinyl alcohol water solution of 7 quality % the preparation polyvinyl alcohol solution.Mix this polyvinyl alcohol solution and this uranyl nitrate mixture and stir the mixture that obtains.Add entry in the mixture that is stirring, this has produced stock liquid.The viscosity of this stock liquid is 5.3 * 10 at 10 ℃
-2Pas (53cP), it is corresponding to being 4.3 * 10 at 15 ℃
-2Pas.
With electric heater PVA is heated to 85 ℃ and remained on approximately this temperature 50 minutes in advance, thereby this thickening material is completely dried.Then, the described exsiccant PVA of weighing.
Utilize the stock liquid fresh feed pump, by the flow adjustment valve with 240cm
3The flow velocity of/min joins the droplets of feed feeder apparatus with the stock liquid that 24L so prepares.From dropping nozzle,, droplets of feed is added in the jar that wherein stores 28% ammonia soln by ammonia atmosphere with the droplets of feed feeder apparatus of 75Hz frequency vibration.Made the ammonium diuranate particle from the drop that drips by nozzle.
Then, so the ammonium diuranate particle of preparation is transferred and puts into the aftertreatment jar.Under the situation that this aftertreatment jar is rotated at 80 ℃ with described particle slaking 1 hour.Through the hot wash of the ammonium diuranate particle of slaking, use 70 ℃ washing with alcohol 30 minutes then with 80 ℃.With the product after the washing 100 ℃ of dryings 3 hours.Obtain the ammonium diuranate particle of drying.
In atmosphere the ammonium diuranate particle of described drying was calcined 3 hours at 550 ℃, it changes the ammonium diuranate particle into the uranium trioxide particle.In the reducing atmosphere of hydrogen/nitrogen mixture gas, the uranium trioxide particle was reduced 3 hours at 600 ℃., made and have highdensity uranium dioxide particle through the reductive product 1550 ℃ of calcinings, described uranium dioxide particulate state class is like pottery.
Described uranium dioxide particle carry out classification particularly particle size select and the sphericity selection after, measure classified uranium dioxide particulate sphericity value.The mean value of sphericity value is 1.04.The productive rate of fuel kernel is 99.1 quality %.
(work embodiment 4)
With with work embodiment 1 in the identical mode of fuel kernel make the fuel kernel particle, in moisture eliminator, store 3 days pva powder as the thickening material except using with silica gel.The viscosity of stock liquid is 5.1 * 10 at 10 ℃
-2Pas (51cP), it is corresponding to being 4.2 * 10 at 15 ℃
-2Pas.The result be fuel kernel particulate average spherical degree be 1.05 with and productive rate be 98.5 quality %.
(comparative example 3)
Make the fuel kernel particle in the mode identical, except use contains the pva powder of 9 quality % moisture as the thickening material with fuel kernel particle among the work embodiment 3.The viscosity of stock liquid is 4.4 * 10 at 10 ℃
-2Pas (44cP), it is corresponding to being 3.4 * 10 at 15 ℃
-2Pas.The result be fuel kernel particulate average spherical degree be 1.08 with and productive rate be 92 quality %.
The fuel kernel particle with good sphericity of preparation has excellent productive rate in work embodiment 3 and 4, and those that prepare in comparative example 3 then have weaker productive rate.The applicant thinks that this difference is to be caused by the following fact: PVA is not by accurate weighing, and the quantity of the PVA of use is less than the quantity that should be added into, and this has reduced the viscosity that is used to produce ammonium diuranate particulate stock liquid of preparation like this.
(work embodiment 5)
Be of a size of that 0.3m is long, 0.3m is wide and the stainless cylinder of steel of high 0.5m with NOx gas treatment equipment and well heater in, put into 5.1kg uranous uranic oxide powder.In this jar, add 3.3L nitric acid gradually, thereby nitric acid is 2.3 to the mol ratio of uranium.After add stopping, start well heater, remain on approximately this temperature with the liquid heat to 100 in the jar ℃ and with described liquid.Then, uranous uranic oxide and nitric acid begin reaction.
After 90 minutes, the uranous uranic oxide powder dissolves fully, does not observe undissolved resistates in the solution in jar in the reaction beginning.
(comparative example 4)
Putting into 5.1kg uranous uranic oxide powder in the employed identical jar with work among the embodiment 5.In this jar, add 2.9L nitric acid gradually, thereby nitric acid is 2.05 to the mol ratio of uranium.After add stopping, start well heater, remain on approximately this temperature with the liquid heat to 100 in the jar ℃ and with described liquid.Then, uranous uranic oxide and nitric acid begin reaction.
After 90 minutes, the uranous uranic oxide powder is dissolving fully not, still has the undissolved resistates of 15g in solution in the reaction beginning.
Claims (17)
1. stock liquid, its viscosity at 15 ℃ is 4.0 * 10
-2-6.5 * 10
-2Pas, it is used to make the ammonium diuranate particle.
2. the stock liquid of claim 1, wherein said stock liquid comprises uranyl nitrate, tetrahydrofurfuryl alcohol and polyvinyl alcohol.
3. one kind prepares the method that is used to make ammonium diuranate particulate stock liquid, described method comprises that mixed nitrate uranyl solution and tetrahydrofurfuryl alcohol are to make the uranyl nitrate mixture, with the water-soluble preparation polyvinyl alcohol water solution of polyvinyl alcohol, this polyvinyl alcohol water solution is mixed with tetrahydrofurfuryl alcohol to prepare polyvinyl alcohol solution and described uranyl nitrate mixture is mixed with described polyvinyl alcohol solution.
4. the method for claim 3, wherein based on the cumulative volume of described stock liquid, the total quantity of polyvinyl alcohol water solution is the 15-20% volume in stock liquid.
5. claim 3 or 4 method, wherein based on the cumulative volume of described stock liquid, the total quantity of tetrahydrofurfuryl alcohol is the 40-50% volume in stock liquid.
6. each method of claim 3-5, wherein the uranyl nitrate mixture is under agitation to carry out with mixing of polyvinyl alcohol solution, is thereafter the degassing and by adding the pure water adjusted volume.
7. each method of claim 3-6, wherein the uranium content in the stock liquid is 0.6-0.9mol-U/L.
8. each method of claim 3-7, wherein when preparing polyvinyl alcohol solution by mix polyethylene alcohol solution and tetrahydrofurfuryl alcohol, tetrahydrofurfuryl alcohol is that minimum being reduced to before 50 ℃ of temperature at polyvinyl alcohol water solution adds.
9. one kind prepares the method that is used to make ammonium diuranate particulate stock liquid, and described stock liquid comprises uranyl nitrate, polyvinyl alcohol water solution and tetrahydrofurfuryl alcohol, and wherein polyvinyl alcohol is to carry out weighing when it is in drying regime.
10. the method for claim 9, wherein said exsiccant polyvinyl alcohol are the polyvinyl alcohol preparations that is absorbed with moisture by heating.
11. the method for claim 9, wherein said exsiccant polyvinyl alcohol is the polyvinyl alcohol that stores with siccative.
12. method for preparing uranyl nitrate solution, described uranyl nitrate solution is used for preparation and is used to make ammonium diuranate particulate stock liquid, thereby described method comprises that making the mol ratio (A/B) of nitric acid and uranium oxide reaction nitric acid (A) and uranium (B) is 2.1-2.6.
13. the method for claim 12, wherein 70-110 ℃ the temperature of being reflected between nitric acid and the uranium oxide is carried out.
14. the method for claim 12 or 13 further comprises the step of the NOx gas that wherein chemical treatment produces in reaction.
15. method for preparing polyvinyl alcohol solution, wherein said polyvinyl alcohol solution is used for preparation and is used to make ammonium diuranate particulate stock liquid, described method comprises that the pure and mild water of mix polyethylene mixes with tetrahydrofurfuryl alcohol with the polyvinyl alcohol water solution of preparation 6-9 quality % with this polyvinyl alcohol water solution.
16. the method for claim 15 wherein is heated under 75 ℃ the situation of temperature polyvinyl alcohol is soluble in water at least at the polyethylene alcohol and water.
17. the method for claim 15 or 16 wherein based on the cumulative volume of the tetrahydrofurfuryl alcohol that contains in the stock liquid, is mixed with polyvinyl alcohol water solution the tetrahydrofurfuryl alcohol of 1-50% volume at least 50 ℃ temperature.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003427059A JP4334334B2 (en) | 2003-12-24 | 2003-12-24 | Method for preparing uranyl nitrate solution |
| JP427059/2003 | 2003-12-24 | ||
| JP230481/2004 | 2004-08-06 | ||
| JP230385/2004 | 2004-08-06 | ||
| JP230327/2004 | 2004-08-06 | ||
| JP298114/2004 | 2004-10-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1922110A true CN1922110A (en) | 2007-02-28 |
| CN100528760C CN100528760C (en) | 2009-08-19 |
Family
ID=34786428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800420341A Expired - Fee Related CN100528760C (en) | 2003-12-24 | 2004-12-22 | Liquid stock for dropping, method for preparing liquid stock for dropping, method for preparing uranyl nitrate solution, and method for preparing polyvinyl alcohol solution |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4334334B2 (en) |
| CN (1) | CN100528760C (en) |
| ZA (1) | ZA200606050B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153143A (en) * | 2011-04-15 | 2011-08-17 | 中核北方核燃料元件有限公司 | Technology method and device for preparing ammonium diuranate |
| CN108182981A (en) * | 2017-12-27 | 2018-06-19 | 中核北方核燃料元件有限公司 | A kind of spherical shape Nuclear Fuel Element Production Line thickener tanning device and its application method |
| CN108389641A (en) * | 2017-12-28 | 2018-08-10 | 中国科学院近代物理研究所 | A kind of preparation facilities and preparation method of nuclear fuel bead |
| CN112687415A (en) * | 2020-11-20 | 2021-04-20 | 中核北方核燃料元件有限公司 | Preparation method of UCO microspheres |
| CN112939084A (en) * | 2019-12-10 | 2021-06-11 | 中核北方核燃料元件有限公司 | Preparation method of fine powder of uranyl nitrate of nuclear purity grade |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2446493C2 (en) * | 2009-08-31 | 2012-03-27 | Российская Федерация в лице Государственной корпорации по атомной энергии "Росатом" (госзаказчик) | Method of producing actinide nitrates |
| RU2626764C1 (en) * | 2016-08-22 | 2017-08-01 | Федеральное государственное унитарное предприятие "Горно-химический комбинат" (ФГУП "ГХК") | Method of dissolving voloxidated irradiated nuclear fuel |
| CA3160213A1 (en) * | 2019-11-04 | 2021-06-17 | X Energy, Llc | Preparation of acid-deficient uranyl nitrate solutions |
| JP7368620B2 (en) | 2019-11-04 | 2023-10-24 | エックス－エナジー， エルエルシー | Preparation of acid-deficient uranyl nitrate solution |
-
2003
- 2003-12-24 JP JP2003427059A patent/JP4334334B2/en not_active Expired - Fee Related
-
2004
- 2004-12-22 CN CNB2004800420341A patent/CN100528760C/en not_active Expired - Fee Related
-
2006
- 2006-07-21 ZA ZA200606050A patent/ZA200606050B/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153143A (en) * | 2011-04-15 | 2011-08-17 | 中核北方核燃料元件有限公司 | Technology method and device for preparing ammonium diuranate |
| CN102153143B (en) * | 2011-04-15 | 2013-01-02 | 中核北方核燃料元件有限公司 | Technology method and device for preparing ammonium diuranate |
| CN108182981A (en) * | 2017-12-27 | 2018-06-19 | 中核北方核燃料元件有限公司 | A kind of spherical shape Nuclear Fuel Element Production Line thickener tanning device and its application method |
| CN108182981B (en) * | 2017-12-27 | 2019-11-22 | 中核北方核燃料元件有限公司 | A kind of spherical shape Nuclear Fuel Element Production Line thickener tanning device and its application method |
| CN108389641A (en) * | 2017-12-28 | 2018-08-10 | 中国科学院近代物理研究所 | A kind of preparation facilities and preparation method of nuclear fuel bead |
| CN112939084A (en) * | 2019-12-10 | 2021-06-11 | 中核北方核燃料元件有限公司 | Preparation method of fine powder of uranyl nitrate of nuclear purity grade |
| CN112687415A (en) * | 2020-11-20 | 2021-04-20 | 中核北方核燃料元件有限公司 | Preparation method of UCO microspheres |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005187220A (en) | 2005-07-14 |
| ZA200606050B (en) | 2007-10-31 |
| CN100528760C (en) | 2009-08-19 |
| JP4334334B2 (en) | 2009-09-30 |
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