CN1948526A - Method of extracting radioactive uranium in phosphate - Google Patents
Method of extracting radioactive uranium in phosphate Download PDFInfo
- Publication number
- CN1948526A CN1948526A CN 200610137762 CN200610137762A CN1948526A CN 1948526 A CN1948526 A CN 1948526A CN 200610137762 CN200610137762 CN 200610137762 CN 200610137762 A CN200610137762 A CN 200610137762A CN 1948526 A CN1948526 A CN 1948526A
- Authority
- CN
- China
- Prior art keywords
- uranium
- acid salt
- solution
- phosphoric acid
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Fertilizers (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
A method to extract uranium with radioactivity from phosphate, content of which is as follows: (1) Acidification. (2) Condensate is separated and washed. (3) Suspended substance is eliminated. (4) Fine filtration. (5) U4+ is oxidized to U6+. (6) Uranium is extracted and separated in organic solvent. (7) U6+ is deoxidized to U4+ and U4+ acid solution is separated. (8) Acid solution is contacted with oxidant and translated to U6+ acid solution. (9) Second-level extraction is carried in organic solution to get second-level raffinate of U6+. (10) Ammonia-uranium base and three carbon alloy can be separated and produced by meeting with amido-carbonate solution. (11) 2-ethylhexyl phosphoric acid is formed by mixing with organic solvent which is non-water soluble. (12) Acidification. (13) DEPA wax is separated. (14) Uranium-base peroxide is created by hydrogen peroxide of water-soluble acid composing to deposit and separate. Extraction of uranium from fertilizer 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 phosphoric acid salt, 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.
Summary of the invention
The present invention extracts radioactive uranium from phosphoric acid, various phosphate fertilizer and composite fertilizer, not only developed new uranium resources, also makes phosphor resource obtain comprehensive utilization and has substantially improved the radiocontamination that the phosphate fertilizer that contains radioactive substance causes the soil environment.
A kind of method of extracting radioactive uranium from phosphoric acid salt comprises following steps successively:
(1) phosphoric acid salt is dissolved in sulfuric acid;
(2) with the acid solution cooling of making in (1), separating, washing cured article;
(3) remove organic and inorganic suspended substance;
(4) carry out fine filtering or RO membrane filtration;
(5) with oxygenant with U
4+Be oxidized to U
6+
(6) extraction separation uranium in DEPA and TOPO organic solvent;
(7) with gained acid solution and dissolved Fe in (6)
2+Contact, U
6+Be reduced into U
4+, and isolate the U of generation
4+Acid solution;
(8) make U
4+Acid solution contacts with oxygenant, changes into U
6+Acid solution;
(9) in DEPA and TOPO organic solvent, carry out secondary and extract, separate the U that produces
6+The secondary extraction liquid;
(10) gained secondary extraction liquid in (9) 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;
(11) described water-soluble Ammonia-uranium base and C3compounds mix with water-insoluble organic solvent, form the 2-ethylhexyl phosphoric acid;
(12) acidifying, formation pH value are 2 acid solution;
(13) isolate the DEPA wax;
(14) with water soluble acid mixing pH at 3.5～4.5 hydrogen peroxide, generate uranium base superoxide, carry out precipitate and separate.
Wherein, removing method organic and inorganic suspended substance described in (3) has: polymerization, carbon filter or zeolite filters.
(7) contain Fe in every liter of the acid solution described in
2+25g～45g.
(7) 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: the unconventional resource method of extracting radioactive uranium from phosphoric acid salt among the present invention has feasibility technically; In addition, production principle is as other industrial byproducts, as long as consider to reclaim the marginal cost that needs, and need not consider to explore, the investment and the cost of mining and ore dressing, thereby reduced uranium production cost and risk, shortened PROJECT TIME; Next, the inventive method adopts and reclaims resource, extracts uranium and can reduce environmental pollution from fertilizer, helps environmental protection, and owing to China's energy shortage, it is a kind of effective save energy method that unconventional resource is got the uranium method simultaneously.
Description of drawings
Fig. 1 is the existing common process schema of uranium mining and processing;
Fig. 2 is the schema of SEPARATION OF URANIUM;
Fig. 3 is the schema of solution purification and extraction uranium;
Fig. 4 is that organism is peeled off schema;
Fig. 5 is the precipitation schema of uranium.
Embodiment
Now reaching the embodiment that extracts radioactivity uranium from phosphate ores in conjunction with the accompanying drawings is described in further detail the inventive method.
Usually phosphate rock main application is as producing phosphatic fertilizer.With reference to the flow process of figure 2, at first dig up mine and preparation of ore obtains phosphate rock, prepare phosphoric acid (being phosphoric acid by wet process usually) through the vitriolic acidifying again.Through solid-liquid separation with after cleaning, will contain uranic acid and separate, the remaining solid residue is further handled.May comprise a large amount of uranium in the phosphate rock, roughly between 0.1～0.5 pound per ton, more general usually content is between 0.2～0.4 pound per ton for its content.Uranium dissolving back (promptly in phosphoric acid by wet process) contains that the content of uranium is about between every liter of 0.15g～0.25g in the uranic acid.This acidization can circulate and carry out, to improve the transformation efficiency of uranium.
The method key that reclaims uranium from phosphoric acid by wet process is 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 3 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 4 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 5 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 (9)
1. method of extracting radioactive uranium from phosphoric acid salt is characterized in that comprising successively following steps:
(1) phosphoric acid salt is dissolved in sulfuric acid;
(2) with the acid solution cooling of making in (1), separating, washing cured article;
(3) remove organic and inorganic suspended substance;
(4) carry out fine filtering or RO membrane filtration;
(5) with oxygenant with U
4+Be oxidized to U
6+
(6) extraction separation uranium in DEPA and TOPO organic solvent;
(7) with gained acid solution and dissolved Fe in (6)
2+Contact, U
6+Be reduced into U
4+, and isolate the U of generation
4+Acid solution;
(8) make U
4+Acid solution contacts with oxygenant, changes into U
6+Acid solution;
(9) in DEPA and TOPO organic solvent, carry out secondary and extract, separate the U that produces
6+The secondary extraction liquid;
(10) gained secondary extraction liquid in (9) 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;
(11) described water-soluble Ammonia-uranium base and C3compounds mix with water-insoluble organic solvent, form the 2-ethylhexyl phosphoric acid;
(12) acidifying, formation pH value are 2 acid solution;
(13) isolate the DEPA wax;
(14) 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 phosphoric acid salt according to claim 1 is characterized in that: removing method organic and inorganic suspended substance described in (3) has: polymerization, carbon filter or zeolite filters.
3. the method for extracting radioactive uranium from phosphoric acid salt according to claim 1 is characterized in that: contain Fe in every liter of the acid solution described in (7)
2+25g～45g.
4. the method for extracting radioactive uranium from phosphoric acid salt according to claim 1 is characterized in that: isolated U in (7)
4+Contain Fe in the acid solution in every liter
2+14g～17g.
5. the method for extracting radioactive uranium from phosphoric acid salt 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.
6. the method for extracting radioactive uranium from phosphoric acid salt according to claim 1, it is characterized in that: the concentration of described amino-carbon acid salt solution is at 0.25M～1.0M.
7. the method for extracting radioactive uranium from phosphoric acid salt 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.
8. the method for extracting radioactive uranium from phosphoric acid salt 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 ℃.
9. the method for extracting radioactive uranium from phosphoric acid salt according to claim 1, it is characterized in that: described non-water-soluble organic solvent is a kerosene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101377621A CN100400687C (en) | 2006-10-30 | 2006-10-30 | Method of extracting radioactive uranium in phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101377621A CN100400687C (en) | 2006-10-30 | 2006-10-30 | Method of extracting radioactive uranium in phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1948526A true CN1948526A (en) | 2007-04-18 |
| CN100400687C CN100400687C (en) | 2008-07-09 |
Family
ID=38018150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101377621A Expired - Fee Related CN100400687C (en) | 2006-10-30 | 2006-10-30 | Method of extracting radioactive uranium in phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100400687C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102455429A (en) * | 2010-10-27 | 2012-05-16 | 核工业北京地质研究院 | Method for measuring uranium in uranium ore |
| 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 |
| CN105181408A (en) * | 2015-09-15 | 2015-12-23 | 中国原子能科学研究院 | Double-effect leaching agent for trace uranium sample pretreatment |
| 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 |
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 |
-
2006
- 2006-10-30 CN CNB2006101377621A patent/CN100400687C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102455429A (en) * | 2010-10-27 | 2012-05-16 | 核工业北京地质研究院 | Method for measuring uranium in uranium ore |
| 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 |
| CN105181408A (en) * | 2015-09-15 | 2015-12-23 | 中国原子能科学研究院 | Double-effect leaching agent for trace uranium sample pretreatment |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100400687C (en) | 2008-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102011020B (en) | Method for recovering rare earth elements from neodymium-iron-boron wastes | |
| CN106367622B (en) | It is a kind of using aluminum sulfate as the ion adsorption type re efficient green extracting method of leaching agent | |
| CN103695671B (en) | Reclaim in a kind of spent acid by producing zirconates, the method for purification Scium trioxide powder | |
| CN104745823B (en) | Method for recycling lithium from waste lithium ion battery | |
| CN104928475B (en) | A kind of recovery method of the aluminium scrap silicon containing rare earth | |
| CN1064110A (en) | The treatment process of ores containing rare earths | |
| CN114377860B (en) | Resource utilization method for chloridized dust collection slag of titanium dioxide by chloridizing method | |
| CN101037285A (en) | Integrative recovering and reusing of heavy metals in wire board plating wastewater treatment sludge | |
| CN102051477A (en) | Method for chemically separating bastnaesite and urdite from mixed rare earth concentrate | |
| CN102061382A (en) | Method for recycling zinc from zinc leaching slag cleaning solution | |
| CN112359232A (en) | Ion adsorption type rare earth extraction method using calcium chloride as leaching agent | |
| CN109439929B (en) | Method for decomposing wolframite and wolframite mixed ore by alkaline system | |
| CN103160689A (en) | Method of iron extraction and removal with solvent extraction agent | |
| CN102732731A (en) | Method for extracting valuable metals and refining zinc sulphate monohydrate from zinc-containing waste material | |
| CN100387734C (en) | Method of extracting radioactive uranium in fly ash | |
| CN106636614A (en) | Method for leaching niobium, scandium and rare earth elements from tailings | |
| CN103352130A (en) | Scandium combined extraction method from red mud and titanium dioxide waste liquid | |
| CN102327809B (en) | Method for removing magnesium oxide from collophanite | |
| CN106367620A (en) | Method for extracting and recycling rare earth from low-content rare earth solution with primary amine extracting agent | |
| CN100400687C (en) | Method of extracting radioactive uranium in phosphate | |
| CN111575485A (en) | Recovery processing method for reducing radioactivity of rare earth slag | |
| CN1023693C (en) | Process for extracting vanadium pentoxide from stone coal ash | |
| CN104402062A (en) | Method for preparing ferric chloride from pyrite cinder | |
| CN107983529B (en) | Method for extracting rare earth from deep sea sediment | |
| CN103773953B (en) | A kind of method adopting the low rare earth concentration elutant of ion exchange method enrichment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080709 Termination date: 20131030 |