CN114350945A - Method for separating and recycling molybdenum back-extraction triphase materials in uranium molybdenum ore hydrometallurgy - Google Patents
Method for separating and recycling molybdenum back-extraction triphase materials in uranium molybdenum ore hydrometallurgy Download PDFInfo
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- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 149
- 239000011733 molybdenum Substances 0.000 title claims abstract description 149
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000000605 extraction Methods 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 50
- KTEXACXVPZFITO-UHFFFAOYSA-N molybdenum uranium Chemical compound [Mo].[U] KTEXACXVPZFITO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims description 15
- 238000004064 recycling Methods 0.000 title abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 93
- 239000000126 substance Substances 0.000 claims abstract description 74
- 239000012071 phase Substances 0.000 claims abstract description 70
- 239000012074 organic phase Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000012065 filter cake Substances 0.000 claims abstract description 27
- 238000002386 leaching Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000002893 slag Substances 0.000 claims description 24
- 229910052770 Uranium Inorganic materials 0.000 claims description 22
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- -1 molybdenum metals Chemical class 0.000 claims description 10
- 238000003916 acid precipitation Methods 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052785 arsenic Inorganic materials 0.000 description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 3
- MIIQUCFATSFCBP-UHFFFAOYSA-L azanium;magnesium;trioxido(oxo)-$l^{5}-arsane Chemical compound [NH4+].[Mg+2].[O-][As]([O-])([O-])=O MIIQUCFATSFCBP-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000391 magnesium silicate Substances 0.000 description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 description 3
- 235000019792 magnesium silicate Nutrition 0.000 description 3
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052567 struvite Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 108010057081 Merozoite Surface Protein 1 Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DFYUJDQOIIPIEI-UHFFFAOYSA-N [NH4+].[OH-].[Mo] Chemical compound [NH4+].[OH-].[Mo] DFYUJDQOIIPIEI-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of uranium molybdenum ore hydrometallurgy, and relates to a method for separating and recycling a molybdenum back-extraction triphase object in uranium molybdenum ore hydrometallurgy, which comprises the following steps: putting the qualified molybdenum back-extraction liquid discharged from the water phase outlet of the molybdenum back-extraction mixed clarifier into a buffer tank to obtain qualified molybdenum liquid containing a triphase object; carrying out preliminary solid-liquid separation, and washing the filtered three-phase substance filter cake by clear water; uniformly mixing the washed triphase substance filter cake with uranium molybdenum ore leaching pulp, leaching by a sulfuric acid method, and performing subsequent extraction and back extraction on the leachate; conveying the solution containing the organic phase and the water phase, which is subjected to solid-liquid separation and washing and then is subjected to precipitate removal, into a clarifier for standing and layering; mixing the organic phase after standing and layering with the poor organic phase of molybdenum back extraction, and performing subsequent extraction process; and (4) conveying the water-phase qualified molybdenum liquid subjected to standing and layering to a purification process to prepare an ammonium molybdate product. The invention effectively destroys the structure of the triphase substance, and fully separates and recovers the organic phase, the water phase and the solid phase.
Description
Technical Field
The invention belongs to the technical field of uranium molybdenum ore hydrometallurgy, and particularly relates to a method for separating and recycling three-phase substances generated by ammonia water molybdenum back extraction in main process flows of acid leaching and amine extraction of primary uranium molybdenum ore.
Background
Molybdenum is a traditional dominant mineral resource in China, the application field of molybdenum is continuously expanded along with the development of economy in China, the molybdenum industry is rapidly developed, the demand of various industries on molybdenum and molybdenum products is continuously increased, and molybdenum is taken as a strategic mineral resource, although the current reserves are abundant, the non-reproducibility of molybdenum determines that the molybdenum cannot be extracted by simply relying on the unregulated exploitation from natural ore, the smelting technology must be improved, and the comprehensive recycling of the molybdenum resource is increased. Most of molybdenum resources in China are common and associated molybdenum ores, the ore dressing pressure is high, according to statistics, molybdenum is taken as an ore deposit of a single mineral product, the storage capacity of the ore deposit only accounts for 14% of the total storage capacity of the molybdenum in the whole country, and in order to make up for the decreasing high-grade molybdenum resources and adapt to the poor hybridization trend of the molybdenum resources, molybdenum extraction technology research aiming at low-grade complex molybdenum ores and molybdenum secondary resources is increasing. The uranium and molybdenum associated ore belongs to one of complex molybdenum ores, useful mineral enrichment is difficult to realize by adopting a traditional physical or chemical ore dressing technology, concentrate cannot be prepared, multiple impurity elements are inevitably leached into a system by direct wet smelting of raw ore, and the difficulty of impurity removal, concentration and enrichment is increased in the process of preparing products. The invention provides a method for separating and recycling a triphase object generated in a molybdenum back-extraction link in the hydrometallurgy comprehensive recycling process of uranium and molybdenum associated raw ore.
After uranium and molybdenum raw ore is leached by an acid sulfate method, uranium, molybdenum and some impurity elements are leached into solution, organic phase prepared from sulfonated kerosene, tri-aliphatic amine and tributyl phosphate is used for uranium and molybdenum step-by-step extraction, acidified water is used for acid washing of the molybdenum-loaded organic phase to remove uranium, ammonia water is used for back extraction of the acid-washed molybdenum-loaded organic phase to obtain qualified molybdenum liquid, magnesium sulfate is added into the qualified molybdenum liquid under certain process conditions to remove arsenic, phosphorus and silicon impurities in a precipitation form, activated carbon adsorption is used for removing organic matters in the qualified molybdenum liquid and decoloration, and finally concentrated sulfuric acid is added for acid precipitation to obtain an ammonium molybdate product. The process leaching solution contains impurity ions such as arsenic, phosphorus, silicon, iron and the like, enters a molybdenum-loaded organic phase in the extraction process, and can extract part of uranium at the same time, although 99% of uranium is removed in the pickling process, a small amount of uranium still enters the back-extraction process along with the molybdenum-loaded organic phase, precipitates of uranium, arsenic, phosphorus, silicon and iron are generated under the alkaline condition in the ammonia-water-molybdenum back-extraction operation process, solid precipitates are adsorbed and carry an organic phase and a water phase, finally a viscous three-phase substance is formed and mixed with qualified molybdenum liquid to enter the purification and impurity removal process, the three-phase substance has a large occupied volume, a stable structure and viscous property, the density is close to that of the qualified molybdenum liquid, and the separation and recovery difficulty is increased. Leading to a series of process problems: 1. three-phase substances are adsorbed and carry organic phases, so that the loss of the organic phases is caused; 2. impurities of the triphase substances enter a magnesium salt impurity removal and active carbon adsorption process along with the qualified molybdenum liquid, and the impurity removal efficiency is reduced and the consumption of active carbon is increased due to the existence of the triphase substances; 3. if a part of the three-phase substances or organic phases after purification enter the acid precipitation process along with the qualified liquid, the risk of influencing the quality of the ammonium molybdate product exists.
The prior art means for separating and recovering the molybdenum back-extraction triphase materials in the uranium molybdenum ore hydrometallurgy is deficient, and the common treatment method comprises the following steps: chemical method, standing clarification, ultrasonic wave and the like. Removing triphase substances by chemical method, adding NaF and Na2CO3NaCl and other salts can introduce other ions into the production system to influence the product quality and the operation of the main process; the energy consumption for breaking three-phase substances by ultrasonic waves is large, and the three-phase substances contain colloidal substances, so that the emulsion breaking effect is poor; by adopting a standing clarification method, the densities of the three-phase substance and the qualified molybdenum liquid are close, the layering effect of the viscous three-phase substance is poor, and the three-phase substance cannot be effectively separated and recovered.
Disclosure of Invention
The invention aims at solving the problems of resource waste, impurity ion introduction during secondary recovery, high energy efficiency consumption and poor effect in the existing uranium-molybdenum ore wet smelting industrial development, and realizes production, operation and quality improvement, and the problems of high organic phase loss, uranium and molybdenum metal loss, high purifying agent consumption and potential product quality risk caused by the reverse extraction of molybdenum in acid wet smelting of native uranium-molybdenum ore The development idea of increasing efficiency and reducing cost.
The technical scheme for realizing the purpose of the invention is as follows:
a method for separating and recovering a molybdenum back-extraction three-phase material in hydrometallurgy of primary uranium molybdenum ore comprises the following steps:
step 1, putting qualified molybdenum back-extraction liquid discharged from a water phase outlet of a molybdenum back-extraction mixing clarifier into a buffer tank to obtain qualified molybdenum liquid containing a triphase object;
step 2, conveying the qualified molybdenum liquid containing the triphase substances to carry out preliminary solid-liquid separation, washing the filtered triphase substance filter cake with a certain amount of clear water, and further replacing the organic phase and the qualified molybdenum liquid in the triphase substance filter cake;
step 3, uniformly mixing the washed triphase filter cake with uranium molybdenum ore leaching pulp, leaching by a sulfuric acid method, dissolving uranium and molybdenum metals adsorbed and precipitated in triphase slag into leachate, further recovering the uranium and molybdenum metals adsorbed and precipitated in the triphase slag, and performing subsequent extraction and back extraction on the leachate;
step 4, conveying the solution containing the organic phase and the water phase, which is subjected to solid-liquid separation and washing and then is subjected to precipitate removal, into a clarifier for standing and layering, wherein the upper layer is the organic phase, and the lower layer is the qualified molybdenum liquid of the water phase, so that oil-water separation is realized;
step 5, mixing the organic phase subjected to standing layering with the poor organic phase subjected to molybdenum back extraction, and performing a subsequent extraction process to further reasonably utilize the recovered organic phase;
and 6, conveying the water-phase qualified molybdenum liquid subjected to standing and layering to a purification process for removing impurities of magnesium salts and adsorbing by using activated carbon, and then performing acid precipitation to prepare an ammonium molybdate product.
In the step 1, the content of three-phase substances in the qualified molybdenum back-extraction liquid, namely the volume ratio of the dry weight of the three-phase substance slag to the qualified molybdenum liquid, is 1.5-20g/L, and the temperature is 20-40 ℃.
In the step 2, the solid-liquid separation mode adopts negative pressure vacuum filtration or positive pressure diaphragm filter pressing.
The volume mass ratio of the washing clear water amount to the dry weight of the three-phase substance slag in the step 2 is 0.5-5:1, and the washing water temperature is 20-40 ℃.
The mass ratio of the dry weight of the washed three-phase slag to the dry weight of the uranium molybdenum ore leaching ore pulp in the step 3 is 0.02-0.25%.
The mixing mode in the step 3 is mechanical stirring, and the mixing time is 0.5-2 h.
In the step 4, the standing and layering time is 0.5-5 h.
In the step 5, the mixing ratio of the standing layered organic phase to the lean organic phase of the molybdenum back extraction is 0-1: 1.
in the step 6, the oil content in the water-phase molybdenum qualified liquid which is kept standing and layered is below 30 mg/L.
The invention has the beneficial technical effects that:
1. the method adopts a physical technology, does not add any chemical reagent, does not introduce other ions into a production system, and avoids the influence of other ions on the quality of ammonium molybdate products and process production.
2. The method adopts a solid-liquid separation mode of negative pressure suction filtration or positive pressure diaphragm filter pressing, a filter cake is formed on the surface of a filter medium such as filter paper or filter cloth during the filtration process of three-phase substances, most of organic phases adsorbed and carried in the three-phase substances are separated from solid precipitates and colloidal substances under the pressure action of vacuum negative pressure or positive pressure, and qualified molybdenum liquid in the filtrate can also replace part of organic phases adsorbed and carried in the three-phase substances, so that the organic phases are separated from the solid precipitates.
3. The method adopts clean water to wash the triphase substance filter cake formed after solid-liquid separation, the clean water disk washing can replace the residual organic phase and molybdenum qualified liquid in the triphase substance filter cake formed on the surface of filter media such as filter paper or filter cloth, etc., further separate the organic phase and molybdenum metal in the triphase substance filter cake, and the organic phase adsorbed and carried by more than 80 percent of triphase substances can be separated from solid precipitates through solid-liquid separation and water washing.
4. The method can trap colloid substances, precipitates and the like in three-phase substances in a filter cake through solid-liquid separation, the quality of an organic phase recovered by standing and layering can meet the process requirement, the organic phase is mixed with a poor organic phase of molybdenum back extraction and then returned to a molybdenum extraction process for use, and the molybdenum back extraction is carried out according to the molybdenum back extractionTaking the difference of the amount of three phases contained in the qualified liquid, wherein the volume of the recovered organic phase can reach 2-15% of the volume of the qualified molybdenum liquid; the oil content in the water-phase molybdenum qualified liquid which is subjected to standing layered recovery can reach below 30mg/L, the adverse effects of three-phase substances on the impurity removal of magnesium salts and the adsorption of active carbon are avoided, the impurity removal, deoiling and decoloring efficiency is improved, the consumption of magnesium sulfate and active carbon is reduced, and the consumption of the powdered active carbon is 20kg/m3And the quality of the acid-precipitated ammonium molybdate product is improved below (the weight of the powdered activated carbon/the volume of the molybdenum qualified liquid), and the chemical grade MSA-1 of the product accounts for more than 95%.
5. The method returns a triphase filter cake obtained after solid-liquid separation and washing by clear water to the front end of the main process flow to be mixed and stirred with the raw ore pulp, reacts the uranium and molybdenum useful metals adsorbed and precipitated in the triphase slag into a solution through an acid leaching process, and recovers more than 90% of the uranium and molybdenum metals in the triphase filter cake.
Drawings
FIG. 1 is a flow chart of a method for separating and recovering a molybdenum strip from uranium molybdenum ore hydrometallurgy.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
Step 1, putting the qualified molybdenum back-extraction liquid discharged from the water phase outlet of the molybdenum back-extraction mixing clarifier into a buffer tank to obtain qualified molybdenum liquid containing triphase substances, wherein the content of the triphase substances (the volume ratio of the dry weight of triphase substance slag to the qualified molybdenum liquid) in the qualified molybdenum back-extraction liquid is 5g/L and the temperature is 25 ℃.
And 2, connecting an experimental device buchner funnel, a filter flask and a vacuum filter, paving qualitative filter paper on the buchner funnel, wetting the filter with clean water, starting the filter, adding 2L of the molybdenum qualified liquid with the triphase substances obtained by back extraction into the buchner funnel for negative pressure suction filtration of-650 mmHg, wherein the suction filtration time is about 40min, no obvious liquid is on the surface of the triphase substance filter cake, adding 50ml of clean water at 25 ℃ after the filtrate is subjected to suction filtration, and continuing the suction filtration until no obvious liquid is on the surface of the triphase substance filter cake, and at the moment, 89% of organic phases adsorbed and entrained in the triphase substances can enter the filter flask at the lower part of the buchner funnel along with the molybdenum qualified liquid and the washing water.
And 3, mechanically stirring and mixing the washed triphase substance filter cake and uranium molybdenum ore leaching pulp for 1h, wherein the ratio of the dry weight of triphase substance slag to the dry ore of the uranium molybdenum ore pulp is 0.05%, adding concentrated sulfuric acid for acid leaching, reacting and dissolving 95% of uranium and molybdenum metals adsorbed and precipitated in the triphase substance slag with sulfuric acid to enter leachate, and performing subsequent extraction and back extraction on the leachate.
And 4, transferring the solution containing the organic phase and the water phase, which is subjected to solid-liquid separation and washing and is subjected to precipitate removal, into a clarifier for standing and layering, wherein a separating funnel can be used for replacing the clarifier, the upper layer is the organic phase, the lower layer is the water phase qualified molybdenum liquid, and the layering time is 30min, so that the qualified molybdenum liquid and the organic phase can be well layered.
And 5, mixing the organic phase subjected to standing layering with the lean organic phase subjected to molybdenum back extraction at a ratio of 0.2:1, performing a molybdenum extraction process, wherein all extraction indexes and operation conditions are normal, and the quality of the organic phase subjected to standing layering recovery can meet the process requirements.
Step 6, analyzing and detecting the oil content in the water-phase qualified molybdenum liquid which is kept standing and layered to be 10mg/L, performing a purification process, analyzing and detecting data according to arsenic, phosphorus and silicon in the qualified molybdenum liquid, theoretically adding 1.2 times of excessive magnesium sulfate, removing the arsenic, phosphorus and silicon from the solution in the form of precipitates such as magnesium ammonium arsenate, magnesium ammonium phosphate, magnesium silicate and the like, and then removing the precipitates in the form of 15kg/m3Adding powdered activated carbon (weight of powdered activated carbon/volume of qualified molybdenum liquid) to perform deoiling, decoloring and adsorbing treatment, and adding concentrated sulfuric acid to make the temperature of the solution reach 55-65 ℃ and the pH value reach 2.0 to prepare an ammonium molybdate product.
Example 2
Step 1, putting qualified molybdenum back-extraction liquid discharged from a water phase outlet of a molybdenum back-extraction mixing clarifier into a container such as a beaker and the like to obtain qualified molybdenum liquid containing a triphase object, wherein the triphase object content (the volume ratio of the triphase object slag dry weight to the qualified molybdenum liquid) in the qualified molybdenum back-extraction liquid is 8g/L and the temperature is 30 ℃;
and 2, connecting an experimental device buchner funnel, a filter flask and a vacuum filter, paving qualitative filter paper on the buchner funnel, wetting the filter with clean water, starting the filter, adding 4L of the molybdenum qualified liquid with the triphase substances obtained by back extraction into the buchner funnel for negative pressure suction filtration of-650 mmHg, wherein the suction filtration time is about 2 hours, no obvious liquid is on the surface of the triphase substance filter cake, adding 50ml of clean water at 35 ℃ after the filtrate is subjected to suction filtration, and continuing the suction filtration until no obvious liquid is on the surface of the triphase substance filter cake, wherein 86% of organic phases adsorbed and entrained in the triphase substances can enter the filter flask at the lower part of the buchner funnel along with the molybdenum qualified liquid and the washing water.
And 3, mechanically stirring and mixing the washed triphase substance filter cake and uranium molybdenum ore leaching pulp for 1.5 hours, wherein the ratio of the dry weight of triphase substance slag to the dry ore of the uranium molybdenum ore pulp is 0.1%, adding concentrated sulfuric acid for acid leaching, reacting and dissolving 93% of uranium and molybdenum metals adsorbed and precipitated in the triphase substance slag with sulfuric acid to enter a leaching solution, and performing subsequent extraction and back extraction on the leaching solution.
And 4, transferring the solution containing the organic phase and the water phase, which is subjected to solid-liquid separation and washing and is subjected to precipitate removal, into a clarifier for standing and layering, wherein a separating funnel can be used for replacing the clarifier, the upper layer is the organic phase, the lower layer is the water phase qualified molybdenum liquid, and the layering time is 40min, so that the qualified molybdenum liquid and the organic phase can be well layered.
And 5, mixing the organic phase subjected to standing layering with the poor organic phase subjected to molybdenum back extraction at a ratio of 0.5:1, performing a molybdenum extraction process, wherein all extraction indexes and operation conditions are normal, and the quality of the organic phase subjected to standing layering recovery can meet the process requirements.
Step 6, analyzing and detecting the oil content in the water-phase qualified molybdenum liquid which is kept standing and layered to be 12mg/L, performing a purification process, analyzing and detecting data according to arsenic, phosphorus and silicon in the qualified molybdenum liquid, theoretically adding 1.2 times of excessive magnesium sulfate, removing the arsenic, phosphorus and silicon from the solution in the form of precipitates such as magnesium ammonium arsenate, magnesium ammonium phosphate, magnesium silicate and the like, and then removing the precipitates in the form of 15kg/m3Adding powdered activated carbon (weight of powdered activated carbon/volume of qualified molybdenum liquid) to perform deoiling, decoloring and adsorbing treatment, and adding concentrated sulfuric acid to make the temperature of the solution reach 55-65 ℃ and the pH value reach 2.0 to prepare an ammonium molybdate product.
Example 3
Step 1, putting qualified molybdenum back-extraction liquid discharged from a water phase outlet of a molybdenum back-extraction mixing clarifier into a buffer tank to obtain qualified molybdenum liquid containing triphase substances, wherein the content of the triphase substances (the volume ratio of the dry weight of triphase substance slag to the qualified molybdenum liquid) in the qualified molybdenum back-extraction liquid is 15g/L and the temperature is 35 ℃; the solid-liquid separation and filtration speed is favorable along with the increase of the temperature, but ammonia in the molybdenum qualified liquor with the overhigh temperature volatilizes strongly, the environmental air quality is influenced, the occupational health is not favorable, the ventilation difficulty is increased, and the molybdenum qualified liquor containing three-phase substances in the buffer tank can be directly subjected to solid-liquid separation without temperature regulation.
And 2, conveying the qualified molybdenum liquid containing the three-phase substance to a Jingjin XAYG20/809-U type van-type membrane filter press through a pump for solid-liquid separation, wherein the filtering pressure is 0.5-0.55MPa, after the three-phase substance slag is saturated in a filter press chamber, stopping feeding, feeding clear water from a central hole of the filter press through the pump to wash a three-phase substance filter cake, wherein the volume mass ratio of the washing water quantity to the dry weight of the three-phase substance slag is 2:1, and the washing water temperature is 35 ℃, at the moment, 82% of an organic phase adsorbed and carried in the three-phase substance can enter a buffer tank along with the qualified molybdenum liquid and the washing water, the van-type membrane filter press has a squeezing function, and the residual organic phase and solution in the three-phase substance slag are further separated from the filter cake through mutual squeezing of a membrane plate and a matching plate in the filter press chamber.
And 3, unloading the washed triphase substance filter cake, mechanically stirring and mixing the triphase substance filter cake with uranium molybdenum ore leaching ore pulp for 2 hours, wherein the ratio of the dry weight of triphase substance slag to the dry ore of uranium molybdenum ore pulp is 0.2%, adding concentrated sulfuric acid to carry out acid leaching, wherein the sulfuric acid leaching is a conventional hydrogen peroxide oxidation acid leaching or acid oxygen pressure leaching process, reacting uranium and molybdenum metals adsorbed and precipitated in triphase substance slag into a solution through the leaching process, and further recovering the uranium and molybdenum metals. 91% of uranium and molybdenum metals adsorbed and precipitated in the three-phase slag can react with sulfuric acid to be dissolved and enter the leachate, and the leachate is subjected to subsequent extraction and back extraction and other processes.
And 4, continuously conveying the solution containing the organic phase and the water phase, which is subjected to solid-liquid separation and washing and is subjected to precipitate removal, into a clarifier for standing, wherein the clarifier is provided with a light phase overflow weir at the upper part and a heavy phase weir at the lower part, the organic phase is gradually separated from the water phase along with time extension, the organic phase is arranged at the upper layer, the water phase molybdenum qualified liquid is arranged at the lower layer, the light phase overflow weir is arranged at the upper part of the clarifier, the heavy phase weir is arranged at the lower part of the clarifier, the standing and layering time is 2 hours, and the water phase molybdenum qualified liquid is analyzed and detected to have the oil content of 15 mg/L.
And 5, mixing the organic phase subjected to standing layering with the poor organic phase subjected to molybdenum back extraction in a ratio of 1:1, trapping colloid substances, precipitates and the like in a three-phase substance in a filter cake through solid-liquid separation, conveying the filter cake to a molybdenum extraction process, ensuring that all extraction indexes and operation conditions are normal, and returning the organic phase subjected to standing layering recovery to molybdenum extraction after being mixed with the poor organic phase subjected to molybdenum back extraction.
Step 6, conveying the qualified molybdenum liquid discharged from the heavy phase weir pipeline through the clarifier for layering to a purification process, analyzing and detecting data according to arsenic, phosphorus and silicon in the qualified molybdenum liquid, adding 1.4 times of excessive magnesium sulfate according to theoretical calculation, removing arsenic, phosphorus and silicon from the solution in the form of precipitates such as magnesium ammonium arsenate, magnesium ammonium phosphate, magnesium silicate and the like, and then removing the precipitates at a concentration of 20kg/m3Adding powdered activated carbon (weight of powdered activated carbon/volume of qualified molybdenum liquid) to perform deoiling, decoloring and adsorbing treatment, removing organic matters and decoloring in the qualified molybdenum liquid, and adding concentrated sulfuric acid to make the temperature of the solution reach 55-65 ℃ and the pH value reach 2.0 to prepare an ammonium molybdate product.
The present invention has been described in detail with reference to the drawings and examples, but the present invention is not limited to the examples, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. The prior art can be adopted in the content which is not described in detail in the invention.
Claims (9)
1. A method for separating and recovering a molybdenum back-extraction three-phase material in primary uranium molybdenum ore hydrometallurgy is characterized by comprising the following steps:
step 1, putting qualified molybdenum back-extraction liquid discharged from a water phase outlet of a molybdenum back-extraction mixing clarifier into a buffer tank to obtain qualified molybdenum liquid containing a triphase object;
step 2, conveying the qualified molybdenum liquid containing the triphase substances to carry out preliminary solid-liquid separation, washing the filtered triphase substance filter cake with a certain amount of clear water, and further replacing the organic phase and the qualified molybdenum liquid in the triphase substance filter cake;
step 3, uniformly mixing the washed triphase filter cake with uranium molybdenum ore leaching pulp, leaching by a sulfuric acid method, dissolving uranium and molybdenum metals adsorbed and precipitated in triphase slag into leachate, further recovering the uranium and molybdenum metals adsorbed and precipitated in the triphase slag, and performing subsequent extraction and back extraction on the leachate;
step 4, conveying the solution containing the organic phase and the water phase, which is subjected to solid-liquid separation and washing and then is subjected to precipitate removal, into a clarifier for standing and layering, wherein the upper layer is the organic phase, and the lower layer is the qualified molybdenum liquid of the water phase, so that oil-water separation is realized;
step 5, mixing the organic phase subjected to standing layering with the poor organic phase subjected to molybdenum back extraction, and performing a subsequent extraction process to further reasonably utilize the recovered organic phase;
and 6, conveying the water-phase qualified molybdenum liquid subjected to standing and layering to a purification process for removing impurities of magnesium salts and adsorbing by using activated carbon, and then performing acid precipitation to prepare an ammonium molybdate product.
2. The method for separating and recovering the molybdenum back-extraction triphase materials in the hydrometallurgical process of primary uranium molybdenum ore according to claim 1, wherein in the step 1, the content of the triphase materials in the qualified molybdenum back-extraction liquid, namely the volume ratio of the dry weight of triphase material slag to the qualified molybdenum liquid, is 1.5-20g/L, and the temperature is 20-40 ℃.
3. The method for separating and recovering the native uranium molybdenum ore hydrometallurgical molybdenum strip three-phase material according to claim 1, wherein in the step 2, a solid-liquid separation mode adopts negative pressure vacuum filtration or positive pressure diaphragm filter pressing.
4. The method for separating and recovering the native uranium molybdenum ore hydrometallurgical molybdenum strip triphase object, according to claim 1, is characterized in that the volume-mass ratio of the washing clear water amount to the triphase object slag dry weight in the step 2 is 0.5-5:1, and the washing water temperature is 20-40 ℃.
5. The method for separating and recovering the native uranium molybdenum ore hydrometallurgical molybdenum strip triphase material according to claim 1, wherein the mass ratio of the washed triphase material slag dry weight to the uranium molybdenum ore leaching pulp dry ore is 0.02-0.25%.
6. The method for separating and recovering the molybdenum strip three-phase material in the hydrometallurgical process of the primary uranium molybdenum ore according to claim 1, wherein the mixing mode in the step 3 is mechanical stirring, and the mixing time is 0.5-2 h.
7. The method for separating and recovering the molybdenum strip triphase materials in the hydrometallurgical process of the primary uranium molybdenum ore according to claim 1, wherein in the step 4, the standing and layering time is 0.5-5 h.
8. The method for separating and recovering the native uranium molybdenum ore hydrometallurgical molybdenum back extraction three-phase material according to claim 1, wherein in the step 5, the mixing ratio of the standing layered organic phase to the lean organic phase of the molybdenum back extraction is 0-1: 1.
9. the method for separating and recovering the native uranium molybdenum ore hydrometallurgical molybdenum strip three-phase material according to claim 1, wherein in the step 6, the oil content in the standing and layered water-phase molybdenum qualified liquid is below 30 mg/L.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4423010A (en) * | 1981-07-29 | 1983-12-27 | Aluminium Pechiney | Process for the selective removal of arsenic in the course of the oxidizing attack by means of a carbonated liquor on a uraniferous ore containing same |
| US20030086864A1 (en) * | 2001-05-09 | 2003-05-08 | Balliett Robert W. | Production of pure molybdenum oxide from low grade molybdeniteconcentrates |
| RU2207387C2 (en) * | 2001-07-04 | 2003-06-27 | Государственное унитарное предприятие "Всероссийский научно-исследовательский институт химической технологии" | Method of metals extraction from ores and concentrates |
| CN101323915A (en) * | 2008-07-17 | 2008-12-17 | 北京矿冶研究总院 | Method for extracting molybdenum and nickel from molybdenum-nickel ore by full wet method |
| CN101792852A (en) * | 2009-11-17 | 2010-08-04 | 灵宝市金源矿业有限责任公司 | Processing for recovering low-grade molybdenum oxide concentrate through wet process |
| AU2015202297A1 (en) * | 2009-07-07 | 2015-05-21 | Cytec Technology Corp. | Processes for recovering metals from aqueous solutions |
| WO2015199098A1 (en) * | 2014-06-25 | 2015-12-30 | Jx日鉱日石金属株式会社 | Method for processing copper-containing molybdenum ore |
| CN105567958A (en) * | 2016-01-12 | 2016-05-11 | 东华理工大学 | Extraction separation method for uranium and molybdenum in high uranium and molybdenum ore solution leachate |
| CN105838908A (en) * | 2016-04-08 | 2016-08-10 | 中南大学 | Efficient and clean molybdenum smelting method |
| CN106676291A (en) * | 2016-12-28 | 2017-05-17 | 核工业北京化工冶金研究院 | Method for comprehensively recovering uranium, niobium and tantalum from ore |
| CN110714121A (en) * | 2018-12-13 | 2020-01-21 | 中核沽源铀业有限责任公司 | Method for reducing consumption of organic phase in uranium molybdenum extraction process |
| CN110735051A (en) * | 2019-10-24 | 2020-01-31 | 桂林理工大学 | Method for cleaning and smelting raw materials containing molybdenum |
| US20200399738A1 (en) * | 2018-05-03 | 2020-12-24 | Central South University | Method for clean metallurgy of molybdenum |
-
2021
- 2021-12-31 CN CN202111662458.XA patent/CN114350945B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4423010A (en) * | 1981-07-29 | 1983-12-27 | Aluminium Pechiney | Process for the selective removal of arsenic in the course of the oxidizing attack by means of a carbonated liquor on a uraniferous ore containing same |
| US20030086864A1 (en) * | 2001-05-09 | 2003-05-08 | Balliett Robert W. | Production of pure molybdenum oxide from low grade molybdeniteconcentrates |
| RU2207387C2 (en) * | 2001-07-04 | 2003-06-27 | Государственное унитарное предприятие "Всероссийский научно-исследовательский институт химической технологии" | Method of metals extraction from ores and concentrates |
| CN101323915A (en) * | 2008-07-17 | 2008-12-17 | 北京矿冶研究总院 | Method for extracting molybdenum and nickel from molybdenum-nickel ore by full wet method |
| AU2015202297A1 (en) * | 2009-07-07 | 2015-05-21 | Cytec Technology Corp. | Processes for recovering metals from aqueous solutions |
| CN101792852A (en) * | 2009-11-17 | 2010-08-04 | 灵宝市金源矿业有限责任公司 | Processing for recovering low-grade molybdenum oxide concentrate through wet process |
| WO2015199098A1 (en) * | 2014-06-25 | 2015-12-30 | Jx日鉱日石金属株式会社 | Method for processing copper-containing molybdenum ore |
| CN105567958A (en) * | 2016-01-12 | 2016-05-11 | 东华理工大学 | Extraction separation method for uranium and molybdenum in high uranium and molybdenum ore solution leachate |
| CN105838908A (en) * | 2016-04-08 | 2016-08-10 | 中南大学 | Efficient and clean molybdenum smelting method |
| CN106676291A (en) * | 2016-12-28 | 2017-05-17 | 核工业北京化工冶金研究院 | Method for comprehensively recovering uranium, niobium and tantalum from ore |
| US20200399738A1 (en) * | 2018-05-03 | 2020-12-24 | Central South University | Method for clean metallurgy of molybdenum |
| CN110714121A (en) * | 2018-12-13 | 2020-01-21 | 中核沽源铀业有限责任公司 | Method for reducing consumption of organic phase in uranium molybdenum extraction process |
| CN110735051A (en) * | 2019-10-24 | 2020-01-31 | 桂林理工大学 | Method for cleaning and smelting raw materials containing molybdenum |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114875247A (en) * | 2022-04-27 | 2022-08-09 | 重庆康普化学工业股份有限公司 | Treatment method of three-phase substance in copper extraction process |
| CN114875247B (en) * | 2022-04-27 | 2023-08-15 | 重庆康普化学工业股份有限公司 | Method for treating three-phase substances in copper extraction process |
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