CN1948527A - Method of extracting radioactive uranium in fly ash - Google Patents
Method of extracting radioactive uranium in fly ash Download PDFInfo
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- CN1948527A CN1948527A CN 200610137764 CN200610137764A CN1948527A CN 1948527 A CN1948527 A CN 1948527A CN 200610137764 CN200610137764 CN 200610137764 CN 200610137764 A CN200610137764 A CN 200610137764A CN 1948527 A CN1948527 A CN 1948527A
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000010881 fly ash Substances 0.000 title claims description 25
- VBWSWBQVYDBVGA-NAHFVJFTSA-N uranium-234;uranium-235;uranium-238 Chemical compound [234U].[235U].[238U] VBWSWBQVYDBVGA-NAHFVJFTSA-N 0.000 title claims description 16
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 75
- 239000002253 acid Substances 0.000 claims abstract description 49
- 238000000605 extraction Methods 0.000 claims abstract description 31
- 239000003245 coal Substances 0.000 claims abstract description 16
- UXDAWVUDZLBBAM-UHFFFAOYSA-N n,n-diethylbenzeneacetamide Chemical compound CCN(CC)C(=O)CC1=CC=CC=C1 UXDAWVUDZLBBAM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- XQXQOGLESNOZED-UHFFFAOYSA-N azane;uranium Chemical compound N.[U] XQXQOGLESNOZED-UHFFFAOYSA-N 0.000 claims abstract description 5
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000000284 extract Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000010883 coal ash Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 229910001339 C alloy Inorganic materials 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 230000008569 process Effects 0.000 description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005065 mining Methods 0.000 description 6
- -1 aut Chemical compound 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003077 lignite Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000941 radioactive substance Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000000638 solvent extraction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 239000010882 bottom ash Substances 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 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 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000014347 soups Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003671 uranium compounds Chemical class 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 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 1
- 241000679125 Thoron Species 0.000 description 1
- MKKVKFWHNPAATH-UHFFFAOYSA-N [C].N Chemical compound [C].N MKKVKFWHNPAATH-UHFFFAOYSA-N 0.000 description 1
- HVSXQPSQUAADIU-UHFFFAOYSA-N [U]N Chemical compound [U]N HVSXQPSQUAADIU-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010884 boiler slag Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- DCSRPHQBFSYJNN-UHFFFAOYSA-L disodium 4-[(2-arsonophenyl)diazenyl]-3-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2ccccc2[As](O)(O)=O)c2ccc(cc2cc1S([O-])(=O)=O)S([O-])(=O)=O DCSRPHQBFSYJNN-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 1
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- Extraction Or Liquid Replacement (AREA)
Abstract
A method to extract uranium with radioactivity from breeze, content of which is as follows: (1) Coal is broke, washed, skived and burnt. (2) Remains after burning are acidized. (3) Condensate is separated and washed. (4) Suspended substance is eliminated. (5) Fine filtration. (6) U4+ is oxidized to U6+. (7) Uranium is extracted and separated in organic solvent. (8) U6+ is deoxidized to U4+ and U4+ acid solution is separated. (9) Acid solution is contacted with oxidant and translated to U6+ acid solution. (10) Second-level extraction is carried in organic solution to get second-level raffinate of U6+. (11) Ammonia-uranium base and three carbon alloy can be separated and produced by meeting with amido-carbonate solution. (12) 2-ethylhexyl phosphoric acid is formed by mixing with organic solvent which is non-water soluble. (13) Acidification. (14) DEPA wax is separated. (15) Uranium-base peroxide is created by hydrogen peroxide of water-soluble acid composing to deposit and separate. Extraction of uranium from coal can lower the production cost of uranium and reduce the environmental pollution, which offers an effective method for energy conservation.
Description
Technical field
The present invention relates to a kind of method of from flyash, extracting radioactive uranium.
Background technology
The ordinary method of the development and use uranium ore resource of present domestic employing mainly can be divided into two classes, and a class is the conventional mining industry development process from dig up mine ore dressing and extraction, and another kind of is the original place lixiviation process.
Fig. 1 is the existing common process schema of uranium mining and processing.With reference to figure 1, the exploitation of conventional uranium deposit exactly from the uranium deposit with industrial value, exploits out by strip mining transformation and underground mining mode with uranium ore, again by radioactive sorting, and fragmentation, and grind; Or uranium metal soaked through chemical solution, produce liquid uranium compound, the ore of extraction and uranium solution all will carry out the extraction of uranium and refining at uranium mill.According to different requirements, uranium chemical concentrate of preparing and nuclear straight product have: ammonium diuranate, aut, uranous uranic oxide, uranium dioxide.
The essence of original place lixiviation process (being called for short ground leaches) exploitation uranium is that by hole-drilling system the control solvent is transferred to liquid phase with uranium in the uranium ore body of natural occurrence condition, rise to face of land processing treatment then.
Production practice prove that leaching reoovery method in ground is adopted smelting process than routine significant advantage:
1) removed exploitation, the broken mill of orebody development roadway engineering and ore and select operation such as smelting mine tailing disposal from, initial cost is few, and building time is short, the labour productivity height, and production cost is low;
2) be easier to realize adopting mechanize of smelting total system and automatization, ground soaking system and test operator's work and sanitary condition have had basic improvement than cutter;
3) be damaged hardly in ground, agroforestry produced influence lack, and helps environment protection:
4) ore body that some disperses, grade is low or geologic condition is complicated, with the ordinary method exploitation, Technological Economy is infeasible, and often land used leaching reoovery method is economical rationality, thereby can fully reclaim resource.
But the uranium that conventional exploitation and ground leach exploitation all needs further to extract and purifying.From ore, extract uranium and in addition purifying generally to pass through leaching, solid-liquid separation, ion-exchange or operations such as drip washing extraction, precipitation, drying and calcining, can make " yellow cake " the final uranium product that can on market, sell.
The domestic exploitation that in the exploitation of uranium, only concentrates on conventional uranium ore at present.And the whole world is facing the common issue with of resource scarcity, and this conventional exploitation can't satisfy the demands far away.For domestic uranium resources in short supply being carried out strong replenishing, the present invention promptly extracts radioactive uranium with unconventional method development and use radioactivity uranium ore from flyash.New uranium resources has not only been developed in this invention, also makes coal resource obtain comprehensive utilization and has substantially improved the radiocontamination that the flyash that contains radioactive substance causes environment.
More domestic experts have done some researchs to flyash and with the building material product that flyash is made to the radiation effect of environment.After radionuclide followed flyash and flue dust to discharge into the atmosphere in the coal, human body mainly was subjected to:
(1) from the external radiation exposure of radioactive substance in the smoke, mists and clouds and atmogenic deposit material (submergence irradiation and ground irradiation);
(2) internal radiation that smoke, mists and clouds sucks and the radioactive substance of resuspending in atmosphere sucks;
(3) radioactive substance is through the transfer of terrestrial environment to people's food chain, it is generally acknowledged that carrying the burning effluent by gas is main exposure pathways through the external radiation exposure that atmospheric dispersion and deposition process cause.
The residuum of coal productions such as coal gangue, fly ash in electric power plant, boiler slag, use, produced cement, brick and tile, ornamental brick etc. by comprehensive utilization, approaching greatly with crowd's distance, and radionuclide wherein often is higher than natural materialss such as timber, clay, one near the space of sealing to the people produce ray and radon, thoron irradiation, dosage generally is outdoor 2～3 times, can reach more than 10 times individually.And the report that has repeatedly carcinogenic sickness rate significantly to raise.
Summary of the invention
The present invention extracts radioactive uranium from flyash, not only developed new uranium resources, also makes flyash obtain comprehensive utilization and has substantially improved the radiocontamination that the flyash that contains radioactive substance causes atmospheric environment.
A kind of method of extracting radioactive uranium from flyash is characterized in that comprising successively following steps:
(1) coal of exploiting out is carried out fragmentation, coal washing, grinding and burning;
(2) combustion residue is dissolved in sulfuric acid;
(3) with the acid solution cooling of making in (2), separating, washing cured article;
(4) remove organic and inorganic suspended substance;
(5) carry out fine filtering or RO membrane filtration;
(6) with oxygenant with U
4+Be oxidized to U
6+
(7) extraction separation uranium in DEPA and TOPO organic solvent;
(8) with gained acid solution and dissolved Fe in (7)
2+Contact, U
6+Be reduced into U
4+, and isolate the U of generation
4+Acid solution;
(9) make U
4+Acid solution contacts with oxygenant, changes into U
6+Acid solution;
(10) in DEPA and TOPO organic solvent, carry out secondary and extract, separate the U that produces
6+The secondary extraction liquid;
(11) gained secondary extraction liquid in (10) is contacted with the water-based amino-carbon acid salt solution of dilution, isolate the water-soluble Ammonia-uranium base and the C3compounds of generation;
(12) described water-soluble Ammonia-uranium base and C3compounds mix with water-insoluble organic solvent, form the 2-ethylhexyl phosphoric acid;
(13) acidifying, formation pH value are 2 acid solution;
(14) isolate the DEPA wax;
(15) with water soluble acid mixing pH at 3.5～4.5 hydrogen peroxide, generate uranium base superoxide, carry out precipitate and separate.
Described coal generates coal ash after burning, use sulfuric acid acidation again.
(4) removing method organic and inorganic suspended substance described in has: polymerization, carbon filter or zeolite filters.
(8) contain Fe in every liter of the acid solution described in
2+25g～45g.
(8) isolated U in
4+Contain Fe in the acid solution in every liter
2+14g～17g.
The Vanadium Pentoxide in FLAKES that contains weight 28%～32% in described DEPA and the TOPO organic solvent.
The concentration of described amino-carbon acid salt solution is at 0.25M～1.0M.
Described secondary extraction liquid is to be that the water-based amino-carbon acid salt solution of 8.2～8.5 dilution mixes with the pH value.
Described secondary extraction liquid be with water-based amino-carbon acid salt solution blended temperature be 40 ℃～50 ℃.
Described non-water-soluble organic solvent is a kerosene.
Compared with prior art, the invention has the beneficial effects as follows: among the present invention with flyash as raw material, as long as consider to reclaim the marginal cost that needs, and need not consider exploration, the investment and the cost of mining and ore dressing can make refuse nugatory, that take up an area of, contaminate environment be utilized, thereby reduced uranium production cost and risk, shortened PROJECT TIME; Simultaneously, extract uranium and can reduce environmental pollution from the coal ash of flying dust or chimney discharge, for environmental protection provides a kind of novel method, because China's energy shortage, it is a kind of method of great practical value that this unconventional resource is got the uranium method.
Description of drawings
Fig. 1 is the existing common process schema of uranium mining and processing;
Fig. 2 is the schema of solution purification and extraction uranium;
Fig. 3 is that organism is peeled off schema;
Fig. 4 is the precipitation schema of uranium.
Embodiment
Now reaching the embodiment that extracts radioactivity uranium from flyash in conjunction with the accompanying drawings is described in further detail the inventive method.
Embodiment 1 coal
Contain a certain amount of uranium in the coal, wherein major part exists with the solid coal ash form after burning." bottom ash " that extracts in " flying dust " that most coal combustion process manufacturing recovers from air-flow and the fire trough.Uranium is to be distributed in flying dust and the bottom ash with being certain proportion.Therefore, leaching process should relate to the coal ash of two kinds of forms.
The extraction of uranium is preferably carried out in the series reaction jar of mineral acid is housed.Sulfuric acid is because its low cost, easily getting property and the convenient property of handling, as the common acid of selecting for use.The serial reaction jar is then as going to optimize duration of contact in the acidleach process and uranium farthest being dissolved.
Mud after the acidleach uses separation and the mixing of carrying out adverse current in a series of jar usually again through cleaning, or the filtration of adverse current, with maximized recovery uranium with reduce the content of acid and uranium in rest solution.The solid residuum can be used as relevant non-cement binder with concrete.
The acid solution of the band uranium that produces from cleaning process need carry out further purifying to remove impurity.This process can be carried out gravity separation then by adding high molecular flocculation agent earlier to form blocky suspended solids, adds fine grain activated carbon simultaneously.The refuse that in the coal tar process of jihuokeli shape, produces, and carry out fixed bed or fluidized-bed reaction with the coal tar of jihuokeli shape, simultaneously with zeolite at fixed bed or fluidized-bed reacts or membrane filtration.
Embodiment 2 brown coal
The fuel value of brown coal, ash component and water-content are all variant, and what therefore have can be used as fuel, and what have is not all right.If a kind of brown coal can be used for burning effectively, the process of therefrom extracting uranium just is similar to the above-mentioned method of extracting from coal.But most brown coal are low fuel compositions, can not be used as electric power or utilization of steam.This material preferably as firing with extraction uranium, can be handled in fluidized-bed.
Brown coal after firing earlier with in or weakly acidic solution reaction, filter then.Wherein filtering is solution to be carried out purifying extract uranium.Solid shape body after the filter carries out acidifying by strong acid solution, and acidifying solution is again by reverse toppling over, and then filtration.Be for further processing, be recycled to the neutral solution of beginning from the neutral or weak property acid that mixes and sepn process produces.Acidization should be carried out the reaction more than two hours 80 ℃ of temperature in retort.
In the description as above Treatment of Coal Ash process, the fs that contains uranium solution needs further purifying to remove impurity before solution extraction after filtering.This step can be carried out gravity separation again by adding high molecular polymer flocculant to form blocky suspended solid, wherein adds tiny activated carbon.The refuse that in the coal tar process of jihuokeli shape, produces, and carry out fixed bed or fluidized-bed reaction with the charcoal of jihuokeli shape, simultaneously with zeolite at fixed bed or fluidized-bed reacts or membrane filtration.In addition, can add acid for optimizing solvent extraction.
More than among two embodiment, after coal ash carried out acidifying, the key that reclaims uranium was in solvent extraction process uranium to be converted to organic state, separates from organic state again, reclaims at last.Guaranteeing does not simultaneously have the phosphoric acid by wet process of uranium can form different phosphorated fertilizer products.
Schema with reference to figure 2 solution purifications and extraction uranium contains uranic acid and need be further purified to guarantee to remove other impurity before solvent extraction.This process can add bentonite, high molecular polymer flocculation agent or inorganic additive (such as wilkinite) forming bulk, and then carries out gravity separation, also can add the particulate activated carbon therein.After handling through above removal of impurities process, the part acid sludge is removed, this part acid sludge can filter or acidifying to utilize again.Contain uranium solution after the purification that produces, next carry out the polishing of the first step solution, utilize carbon post or zeolite column to react, carry out last solution again and polish loose film RO micro-filtration.
Carry out oxidation through the uranic acid that contains behind these scavenging process with hydrogen peroxide, with U
4+Change into U
6+Form.Usually oxidizing reaction can be in a blended retort, reaction 5～10min.Oxygenant in this step can also be selected sodium oxymuriate, air etc. for use.The amount of oxygenant should be enough to guarantee with U
4+The uranium that form exists changes into U
6+Form exists.In general, the amount of oxygenant is by weight from 0.01%～0.03%.
If acidifying has been finished, or the acid that has generated is in the condition of high temperature, and cools off, and should cool off before main solvent extraction process.More effective for the extraction that makes the uranium that carries out subsequently, need be cooled to 40 ℃～50 ℃ to acid solution.
Next the uranium solution that contains through above-mentioned processing extracts, and contacts with insoluble organic extracting solution, and uranium is converted to organic state, extracts the uranium-bearing organism.Extraction agent among the present invention is 2-ethylhexyl phosphoric acid (DEPA) and the oxide compound (TOPO) that is dissolved in a kind of organic solvent (as kerosene).It with contain uranium solution and contact after, uranium ion changes into UO
2+The mixture of-DEPA.Contain the DEPA of about every liter of 0.1～1MOL and the TOPO of about every liter of 0.025～0.25MOL in general this extraction agent.Roughly in 0.1～10 scope, be 1～5min duration of contact to the capacity ratio of acid and solvent, and Best Times is 2～3min.Raffinate after the extraction can clean again again and utilize.
With reference to the schema that figure 3 organism are peeled off, the uranium-bearing organism of extraction will be peeled off, and makes uranium become mineralized again from organic state.Hexavalent uranium and Fe
2+Contact makes uranium change water-soluble attitude over to.In this process, ferrous ion is oxidized to iron ion, and the uranium-bearing organism becomes U
4+Ion.
Uraniferous stripping solution need reoxidize process through one, and wherein oxygenant can also be selected hydrogen peroxide or above-mentioned other oxygenants.In this process, the uranous in the solution transforms hexavalent uranium.Uranium after the oxidation one with the reverse extracting system of initial extracting system in, contact with the DEPA-TOPO extracting solution once more, carry out the secondary solvent extraction, the uranium-bearing organism is extracted again, a part of residual organic substances is mixed with sulfuric acid, extracts recovery again.
The best water of uranium-bearing organism after the second extraction washes away to remove phosphoric acid, organism after washing away has entered the carbon filtration step, the adding sal volatile carries out carbonate to be peeled off, and becomes uranium-bearing carbonate stripping solution, and hexavalent uranium forms soluble amino, uranium base and three carbon complexes.Poor organism can reclaim with sulfuric acid again.
DEPA-TOPO concentrated solution concentration in the extraction system of initial extraction system and secondary is about 0.5MOL DEPA and 0.125MOL TOPO.Use same extracting solution two extraction stages, guaranteed in the entire treatment process, only need a kind of DEPA-TOPO to mix, significantly reduced operational issue.In addition, use same extracting solution that the handiness of in two stages organism being added is provided, realized system is better controlled.Such as the compound that in the initial period, has produced iron, will remove by filter the iron of generation in the use in subordinate phase by described carbon.
In the separating treatment process of phosphoric acid (purpose is farthest to discharge uranium), stripping solution should have the five phosphorus oxide solution (being preferably between 29%～30%) that account for 28%～32% weight ratio greatly, and iron oxide solution every liter of 25g～45g (being preferably between 35g～40g) approximately.
The source of phosphoric acid, the pure acid that can get in the said process initial purification phase concentrates or adds denseer acid on a small quantity, to make required Vanadium Pentoxide in FLAKES concentration.Organism is 0.7: 1 with the ratio of acid.Organism can be recovered in the initial extraction unit again.
Under the perfect condition, ammonia carbon creates in a separation system, is loaded into the separation vessel of alkalescence then as a kind of aqueous solution, and ammonia charcoal concentrated solution is preferably between 0.3M～0.4M below 0.5M.In this process, it is very important strictly controlling pH and temperature.PH value should satisfy from 8.5～9, can increase separating out of iron ion like this.Temperature is 40 ℃～50 ℃, preferably 45 ℃.
With reference to the precipitation schema of figure 4 uranium, uranium-bearing carbonate stripping solution sulfuric acid acidation causes insoluble wax shape DEPA suspended substance to produce, and therefore need remove suspended substance with the organic solvent (as kerosene) of effective quantity before acidization and in the process.In practice, in acid solution, account for 5%～10% DEPA, mix, enter separation phase then, in this stage, adopt air suspension to handle, to remove the insoluble waxy DEPA that in organic process, produces with acidifying solution.
The UO of purifying
2 2+Add hydrogen peroxide in the acid solution, adjust between pH value to 3.5～4.5, to generate uranium base superoxide with ammonia.In the suspension process, uraniferous soup compound is removed, and washing is to isolate amide (being the sulfuric acid diamine).Soup compound subsequently through centrifugally dewater, dry (such as under 110 ℃ of temperature) generate and be fit to the uranium compound that directly utilized by the uranium transforming agent.
The above embodiment only is optimum embodiment of the present invention; the invention is not restricted to the foregoing description; for persons skilled in the art; the any conspicuous change of under the prerequisite that does not deviate from the principle of the invention it being done all belongs to the protection domain of design of the present invention and claims.
Claims (10)
1. method of extracting radioactive uranium from flyash is characterized in that comprising successively following steps:
(1) coal of exploiting out is carried out fragmentation, coal washing, grinding and burning;
(2) combustion residue is dissolved in sulfuric acid;
(3) with the acid solution cooling of making in (2), separating, washing cured article;
(4) remove organic and inorganic suspended substance;
(5) carry out fine filtering or RO membrane filtration;
(6) with oxygenant with U
4+Be oxidized to U
6+
(7) extraction separation uranium in DEPA and TOPO organic solvent;
(8) with gained acid solution and dissolved Fe in (7)
2+Contact, U
6+Be reduced into U
4+, and isolate the U of generation
4+Acid solution;
(9) make U
4+Acid solution contacts with oxygenant, changes into U
6+Acid solution;
(10) in DEPA and TOPO organic solvent, carry out secondary and extract, separate the U that produces
6+The secondary extraction liquid;
(11) gained secondary extraction liquid in (10) is contacted with the water-based amino-carbon acid salt solution of dilution, isolate the water-soluble Ammonia-uranium base and the C3compounds of generation;
(12) described water-soluble Ammonia-uranium base and C3compounds mix with water-insoluble organic solvent, form the 2-ethylhexyl phosphoric acid;
(13) acidifying, formation pH value are 2 acid solution;
(14) isolate the DEPA wax;
(15) with water soluble acid mixing pH at 3.5～4.5 hydrogen peroxide, generate uranium base superoxide, carry out precipitate and separate.
2. the method for extracting radioactive uranium from flyash according to claim 1, it is characterized in that: described coal generates coal ash after burning, use sulfuric acid acidation again.
3. the method for extracting radioactive uranium from flyash according to claim 1 is characterized in that: removing method organic and inorganic suspended substance described in (4) has: polymerization, carbon filter or zeolite filters.
4. the method for extracting radioactive uranium from flyash according to claim 1 is characterized in that: contain Fe in every liter of the acid solution described in (8)
2+25g～45g.
5. the method for extracting radioactive uranium from flyash according to claim 1 is characterized in that: isolated U in (8)
4+Contain Fe in the acid solution in every liter
2+14g～17g.
6. the method for extracting radioactive uranium from flyash according to claim 1 is characterized in that: the Vanadium Pentoxide in FLAKES that contains weight 28%～32% in described DEPA and the TOPO organic solvent.
7. the method for extracting radioactive uranium from flyash according to claim 1, it is characterized in that: the concentration of described amino-carbon acid salt solution is at 0.25M～1.0M.
8. the method for extracting radioactive uranium from flyash according to claim 1 is characterized in that: described secondary extraction liquid is to be that the water-based amino-carbon acid salt solution of 8.2～8.5 dilution mixes with the pH value.
9. the method for extracting radioactive uranium from flyash according to claim 7 is characterized in that: described secondary extraction liquid be with water-based amino-carbon acid salt solution blended temperature be 40 ℃～50 ℃.
10. the method for extracting radioactive uranium from flyash according to claim 1, it is characterized in that: described non-water-soluble organic solvent is a kerosene.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619397B (en) * | 2009-07-17 | 2011-03-16 | 云南佰盾环保新技术咨询有限公司 | Method for recycling uranium from uranium extraction coal residue with wet method |
| CN102603079A (en) * | 2012-03-19 | 2012-07-25 | 中国科学院福建物质结构研究所 | Method for recycling treatment of industrial uranium-containing wastes |
| CN103146938A (en) * | 2013-03-28 | 2013-06-12 | 中国科学院长春应用化学研究所 | Extraction and separation method of uranium |
| CN106319250A (en) * | 2016-09-28 | 2017-01-11 | 华中科技大学 | Method for directional enrichment and extraction of uranium in coal combustion process |
| CN106350146A (en) * | 2016-09-28 | 2017-01-25 | 华中科技大学 | Method for regulating oriented conversion of uranium in coal combustion process |
| CN107805727A (en) * | 2016-09-09 | 2018-03-16 | 核工业北京化工冶金研究院 | A kind of method that uranium is reclaimed from phosphoric acid by wet process |
| CN110983058A (en) * | 2019-12-06 | 2020-04-10 | 核工业北京化工冶金研究院 | Method for leaching uranium in refractory coal fly ash by countercurrent washing alkali method |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57181335A (en) * | 1981-04-30 | 1982-11-08 | Hitachi Ltd | Stripping method for uranium |
| US7192563B2 (en) * | 2003-03-31 | 2007-03-20 | Secretary, Department Of Atomic Energy, Government Of India | Process for recovery of high purity uranium from fertilizer grade weak phosphoric acid |
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| CN101619397B (en) * | 2009-07-17 | 2011-03-16 | 云南佰盾环保新技术咨询有限公司 | Method for recycling uranium from uranium extraction coal residue with wet method |
| CN102603079A (en) * | 2012-03-19 | 2012-07-25 | 中国科学院福建物质结构研究所 | Method for recycling treatment of industrial uranium-containing wastes |
| CN103146938A (en) * | 2013-03-28 | 2013-06-12 | 中国科学院长春应用化学研究所 | Extraction and separation method of uranium |
| CN107805727A (en) * | 2016-09-09 | 2018-03-16 | 核工业北京化工冶金研究院 | A kind of method that uranium is reclaimed from phosphoric acid by wet process |
| CN107805727B (en) * | 2016-09-09 | 2020-03-17 | 核工业北京化工冶金研究院 | Method for recycling uranium from wet-process phosphoric acid |
| CN106319250A (en) * | 2016-09-28 | 2017-01-11 | 华中科技大学 | Method for directional enrichment and extraction of uranium in coal combustion process |
| CN106350146A (en) * | 2016-09-28 | 2017-01-25 | 华中科技大学 | Method for regulating oriented conversion of uranium in coal combustion process |
| CN106350146B (en) * | 2016-09-28 | 2020-05-19 | 华中科技大学 | Method for regulating and controlling directional conversion of uranium in coal combustion process |
| CN110983058A (en) * | 2019-12-06 | 2020-04-10 | 核工业北京化工冶金研究院 | Method for leaching uranium in refractory coal fly ash by countercurrent washing alkali method |
| CN117089730A (en) * | 2023-08-21 | 2023-11-21 | 核工业北京化工冶金研究院 | Recovery method of uranium in broken resin |
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