WO2016054952A1 - 全程无污染排放的钨矿物原料冶金工艺 - Google Patents
全程无污染排放的钨矿物原料冶金工艺 Download PDFInfo
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- WO2016054952A1 WO2016054952A1 PCT/CN2015/087823 CN2015087823W WO2016054952A1 WO 2016054952 A1 WO2016054952 A1 WO 2016054952A1 CN 2015087823 W CN2015087823 W CN 2015087823W WO 2016054952 A1 WO2016054952 A1 WO 2016054952A1
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- leaching
- clinker
- ammonium
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- tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention relates to a method for preparing APT from a tungsten mineral raw material, and belongs to the technical field of tungsten smelting.
- raw material refers to a mixture of tungsten mineral raw materials and ingredients, which are proportioned and ground to a certain fineness.
- the term "clinker” refers to a material obtained by grinding a tungsten mineral raw material, a furnish, mixing it into a raw material, and then baking it at a high temperature.
- mineralizer refers to a substance that accelerates the reaction between the tungsten mineral raw material and the furnish or lowers the calcination temperature during the calcination of the green meal.
- the industrial process for preparing APT mainly comprises the steps of: decomposing a tungsten mineral raw material by caustic soda or soda to obtain a crude sodium tungstate solution; by solution purification-ion exchange or solvent extraction transformation (either by ion exchange or solvent extraction) In addition to impurity and transformation), a pure ammonium tungstate solution is obtained; and then crystallization by evaporation to obtain an APT product.
- the prior art has the following essential defects: both use a non-circulating or semi-circulating process system, and do not implement the full cycle process.
- the prior art has at least the following technical problems: it is necessary to set a waste water discharge port, and the waste water pollution problem cannot be completely eliminated; the auxiliary materials are mostly disposable consumables, and the leaching agent in the leaching process is excessively used, and the auxiliary materials are reacted after the corresponding process steps are completed.
- the auxiliary raw materials are consumed in a large amount, and a large amount of waste water is generated; a large amount of high-salt waste liquid is generated during the transformation of the sodium tungstate solution, and the ammonia liquid waste water is generated by evaporating the crystallization mother liquid.
- a method of preparing APT from a tungsten mineral feedstock comprising the steps of:
- ammonium carbonate-ammonium hydrogencarbonate ammonium carbonate-ammonium tungstate, ammonium carbonate-CO 2 , ammonium carbonate-ammonia-CO 2 , ammonium carbonate-ammonia, ammonium carbonate-ammonium hydrogencarbonate-ammonium tungstate, Ammonium carbonate-ammonium hydrogencarbonate-ammonium tungstate-CO 2 , ammonium carbonate-ammonia water-ammonium tungstate, ammonium carbonate-ammonium tungstate-CO 2 , and/or ammonium carbonate-ammonia-tungstate-CO 2 system leaching material;
- step 4 The leaching slurry is subjected to solid-liquid separation and slag phase washing to obtain a crude ammonium tungstate solution and leaching slag, and part of the leaching slag is returned as an ingredient in step 1) for raw material distribution, and the remaining portion is stored;
- a crystallization mother liquor and a solid phase are obtained, and the solid phase is washed with water and/or an ammonium salt solution, and after drying, the APT product is obtained (or dissolved into the next stage).
- the crystallization mother liquor is returned together with the ammonia and carbon dioxide obtained in step 6) to the leaching step 3) of the clinker, and supplemented with ammonium carbonate consumed (by ammonium bicarbonate or ammonia and CO 2 Partially substituted) after the cycle of leaching clinker.
- the tungsten mineral raw material comprises scheelite, wolframite, black and white tungsten mixed ore, and/or tungsten fine mud; preferably, when the raw material is prepared, the amount of the leaching residue is added according to CaO/ in the raw material.
- the raw material particle size is not particularly limited, preferably not more than 200 ⁇ m, more preferably not more than 100 ⁇ m, more preferably not more than 40 ⁇ m; when the raw meal is calcined, the temperature is not lower than 500 ° C, preferably Is 800-1050 ° C, more preferably 850-950 ° C;
- a mineralizer preferably calcium fluoride, is added during the raw meal formulation to accelerate the reaction between the tungsten mineral feedstock and the furnish, significantly reducing the calcination temperature;
- the calcination time of the raw meal is 0.5-8.0 h, preferably 1.0-3.0 h, more preferably 2.0 h; when the tungsten mineral raw material is scheelite, the calcination atmosphere is not particularly limited, preferably neutral or oxidizing atmosphere;
- the baking atmosphere is a neutral or reducing atmosphere, preferably a neutral atmosphere;
- the particle size of the clinker is not particularly limited, preferably Is not more than 200 ⁇ m, further preferably not more than 74 ⁇ m, and more preferably not more than 45 ⁇ m;
- a part of the CO 2 in the leaching system comes from the furnace (kiln) gas produced by the raw material roasting process or the commercial CO 2 , and the other part comes from the CO 2 produced by the evaporation crystallization process of the ammonium tungstate solution;
- the CO 2 may be introduced during the leaching process or may be introduced prior to leaching.
- the ammonium carbonate concentration in the initial system of leaching is greater than 20 g-(NH 4 ) 2 CO 3 /100 g-H 2 O, preferably the concentration of the saturated solution in the system, and the ammonium hydrogencarbonate is added as a solution or a solid.
- the amount of ammonium hydrogencarbonate added is not particularly limited, and is preferably not less than 1.0 times the amount required to convert calcium in the clinker to CaCO 3 (theoretical amount), more preferably 1.1 to 1.4 times the theoretical amount, and tungsten.
- the concentration of the ammonium acid is not particularly limited as long as it can ensure that the concentration of ammonium tungstate in the solution obtained after the sufficient leaching of the tungsten in the clinker does not exceed the equilibrium concentration under the system, and the amount of the ammonia added is not particularly limited, and the preferred initial leaching is carried out.
- the leaching temperature is not lower than 5 ° C, preferably 10-80 ° C, more preferably 20-70 ° C, more preferably 30-50 ° C;
- the leaching time is not particularly limited as long as it can ensure sufficient leaching of tungsten in the clinker, preferably leaching time is 0.5-8.0 h, more preferably leaching time is 2-5 h; purification decontamination process includes molybdenum removal At least one of phosphorus, tin, arsenic, silicon, iron, sodium, potassium, rubidium, cesium, calcium, and magnesium;
- a system for preparing an APT using the method of claim 1 comprising:
- roasting kiln (furnace)
- the prepared raw material is added to a roasting kiln (furnace) for roasting, and after cooling, clinker is obtained;
- the grinding equipment A is selected from the group consisting of: a vibration mill, a ball mill, a rod mill, a self-grinding mill, a stirring mill, a suspension roller mill, a tower mill, a colloid mill, a centrifugal mill, a high pressure disc Mill, Raymond mill, jet mill.
- the roasting kiln comprises: a static roasting kiln (furnace) and a dynamic roasting kiln (furnace).
- the grinding equipment B is selected from the group consisting of: a roll machine, a vibration mill, a ball mill, a rod mill, a self-grinding machine, a stirring mill, a hanging roll pulverizer, a tower mill, a colloid mill, a centrifugal mill Machine, high pressure disc mill, Raymond mill, jet mill.
- the leaching device may be a single leaching device or 2-4 leaching devices may be used in series.
- the leaching device may be a stirred leaching device or a ball leaching device.
- the leaching apparatus is sealable and capable of withstanding a pressure of 4 atm.
- the filtering device is a suction filtration device, a filter press device, a natural filter tank.
- the impurity removing device is a de-canting tank, a filtering device, a settling tank.
- a stirring device is disposed in the de-mixing tank.
- the tungsten element is changed into a substance which is easily leached by the ammonium carbonate salt solution, thereby achieving low temperature leaching of tungsten, reducing energy consumption and cost in the leaching process, and at the same time, leaching slag can be Recycling as an ingredient in the transformation of tungsten mineral raw materials;
- ammonium carbonate - ammonium hydrogencarbonate - ammonium tungstate or “ammonium carbonate - ammonium tungstate - CO 2 " or “ammonium carbonate - ammonia - ammonium tungstate” or “ammonium carbonate - ammonia” or “carbonic acid” ammonium “or” ammonium carbonate - ammonium bicarbonate "or” ammonium carbonate - ammonia -CO 2 "or” ammonium carbonate - aqueous ammonia - ammonium tungstate -CO 2 "or” ammonium carbonate - ammonium - ammonium tungstate -CO 2 "or ammonium carbonate-CO 2 " or “ammonium carbonate-CO 2 " or “ammonium carbonate - ammonium tungstate” or “ammonium carbonate - ammonium bicarbonate - CO 2 " system is not obvious as a leachate because the weakly alkaline system cannot handle scheelite,
- the tungsten smelting industry currently generally uses a strong acid (such as hydrochloric acid) or a strong alkali (such as sodium hydroxide) system, and leaches tungsten mineral raw materials under high temperature and high pressure environment, and "ammonium carbonate-ammonium hydrogencarbonate-ammonium tungstate", Ammonium carbonate-ammonium tungstate-CO 2 "", “ammonium carbonate-ammonia-ammonium tungstate”, “ammonium carbonate-ammonia”, “ammonium carbonate”, “ammonium carbonate-ammonium hydrogencarbonate", “ammonium carbonate-ammonia-CO” 2 ",” ammonium carbonate - aqueous ammonia - ammonium tungstate -CO 2 ",” ammonium carbonate - ammonium - ammonium tungstate -CO 2 ",” ammonium carbonate -CO 2 ",” ammonium carbonate - ammonium tungstate "and The "ammonium carbonate-ammonium bi
- the leaching system material is converted into ammonia and carbon dioxide after the crystallization step, just
- a good tungsten leaching effect can be obtained not only when the leaching liquid solid is relatively high, but also when the leaching liquid solid ratio is less than 10, the leaching rate of tungsten in the clinker does not decrease, and the concentration of WO 3 in the obtained leaching liquid is still sufficiently industrialized.
- the closed loop process is adopted, and only the waste slag discharge port is provided, and the waste water discharge port is no longer required, and the pollution problem of the waste water discharge is completely eradicated.
- the auxiliary material is no longer a disposable consumable, and the leaching agent in the leaching process is recycled. Even if the auxiliary material is used excessively, it is not directly discharged after the reaction of the corresponding process step, and the corresponding acid or the corresponding acid is no longer needed. The alkali is neutralized, so the auxiliary material consumption is drastically reduced, and the production cost is greatly reduced.
- the cyclic metallurgy process is realized, and the "waste water" of the conventional process system is sucked and squeezed to completely prevent some tungsten elements from being discharged in vain, and therefore, the recovery rate of tungsten elements is also improved.
- a pretreatment step of a tungsten mineral raw material is added, using "ammonium carbonate-ammonium hydrogencarbonate-ammonium tungstate” or “ammonium carbonate-ammonium tungstate-CO 2 " or "ammonium carbonate-ammonia-ammonium tungstate” or “ammonium carbonate - ammonia” or “ammonium carbonate” or “ammonium carbonate - ammonium bicarbonate” or “ammonium carbonate - ammonia -CO 2” or “ammonium carbonate - aqueous ammonia - ammonium tungstate -CO 2” or “ammonium carbonate - Leaching of tungsten mineral clinker with ammonium bicarbonate-ammonium tungstate-CO 2 ” or “ammonium carbonate-CO 2 ” or “ammonium carbonate-ammonium tungstate” or “ammonium carbonate-ammonium bicarbonate-CO 2 ” system, mild leaching conditions
- the process flow is simple, the operation is convenient, the production cost is low, no waste water is discharged, and environmental pollution is reduced to a minimum.
- Figure 1 is a schematic view showing the structure of a system for preparing APT from a tungsten mineral raw material according to the present invention.
- FIG. 2 is a process flow diagram of preparing APT from a tungsten mineral raw material in accordance with the present invention.
- Embodiments of the present invention will be further described below with reference to FIGS. 1-2.
- the metallurgical process of the tungsten-containing mineral raw material of the present invention comprises the following steps:
- the W-containing mineral raw material 100 is mixed with the ingredient MN (M represents a positive ion, N represents a negative ion) into a raw meal 101;
- the raw material 200 is calcined to promote a chemical reaction to transform into a clinker containing M and W ions, thereby obtaining high chemical reactivity of the clinker;
- the leaching slurry is subjected to solid-liquid separation 400 to obtain a crude solution containing A and W ions and a leaching slag containing M, and the slag phase is washed, and the washing liquid is fed back to the clinker leaching step (the first closed loop), and is taken according to actual needs. At least part of the leaching slag is fed back to the raw material configuration section (II closed loop) as an ingredient, and if the leaching residue has a remaining portion, it is stored;
- Performing at least one stage purification and impurity removal 500 on the crude solution containing A and W ions (preferably, the last stage may be provided with a suction device);
- the purified solution is subjected to evaporative crystallization 600 to precipitate an intermediate product containing the W element; at the same time, a step of releasing the gas associated with the element A and the gas associated with the N element to the leaching clinker 300 (the third closed loop) is released. And the evaporated water is fed back to the solid-liquid separation step of the leaching slurry 300 (IV closed loop);
- the crystallization slurry is subjected to liquid-solid separation 700 to obtain a crystallization mother liquor and a solid phase, and the solid phase is washed with water and/or an ammonium salt solution, and after drying, a final product containing a W element is obtained (preferably, the solid phase is again subjected to Dissolving and crystallization to obtain a higher purity final product); and the crystallization mother liquor is also returned to the step of leaching clinker (V-closed loop),
- the process consists of multiple closed loops with no wastewater discharge throughout.
- the metallurgical system of the tungsten mineral raw material of the present invention comprises:
- Raw material preparation device 10 having a mineral raw material inlet 11 and a dosing inlet 12 (preferably also provided with a mineralizer inlet 13; preferably, each inlet is also provided with a meter), a raw material grinding device (including a mixer) 14.
- a roasting kiln (furnace) 20 which is connected to the raw material outlet 15 via a feeding meter and a raw material storage bin, and has a heating device, a heat insulating device (preferably including a cooling device 21), and an atmosphere (oxidizing atmosphere, reducing atmosphere, medium) sexual atmosphere) control device and coarse clinker outlet 22;
- Clinker grinding device 30 which is connected to the clinker outlet 22 via a clinker silo, having a grinder and a fine clinker outlet 31;
- the leaching device 40 is in communication with the fine clinker outlet 31, and has a leaching agent inlet 41, a leaching slurry outlet 42, a feedback gas recovery port 43, a crystallization slurry separation washing liquid recovery port 44, a slag phase washing liquid recovery port 45, and a seed crystal inlet. 46 (preferably, also including a carbon dioxide inlet 47);
- a solid-liquid separation device for leaching the slurry, which is in communication with the leaching slurry outlet 42, a filter scrubber 50 having a leaching residue containing a compounding element, a crude solution outlet 51 containing a tungsten element, a leaching slag feedback port 52, An outlet 53 of the remaining leaching residue storage, a washing liquid feedback outlet 54, and a receiving port 55 for evaporating crystal condensed water, the solid-liquid separating device is fed back to the leaching slag receiving port 16 of the raw material preparing device 10 and the leaching device 40
- the seed crystal inlet 46 is connected;
- At least one stage cleaning and decontaminating device 60 the inlet 61 of the first stage is connected to the crude solution outlet 51 containing tungsten element, each stage has a purifying agent inlet and an impurity collector, and the last stage has a fine solution outlet containing tungsten element. 62 (preferably, the last stage is provided with a suction device);
- the crystallization apparatus 70 has an inlet 71 communicating with the crude solution outlet 62 containing tungsten element, having a crystal slurry outlet 72, a gas feedback port 73 fed back to the leaching device, and a condensate outlet 74 (preferably a crude solution evaporative crystallization control having a tungsten product) Device);
- a liquid-solid separation device 80 for the crystal slurry which is in communication with the crystal slurry outlet 72, having an outlet 81 for returning the crystallization mother liquor to the leaching device 40, a solid phase wash inlet 82, and an outlet 83 for the tungsten product (preferably, with the next stage Dissolution, crystallization, purification subsystem connectivity).
- the tungsten mineral raw material and a certain amount of the calcium-containing material and the mineralizer are ground and uniformly mixed to obtain a raw material; when the raw material is prepared, the calcium-containing substance is added in an amount of CaO/WO 3 in the raw material or (CaO + FeO) / WO 3 or (CaO + MnO) / WO 3 or (CaO + FeO + MnO) / WO 3 molecular ratio of at least 1.0, preferably 1.5-6.0, more preferably 3.0-4.0, more preferably Is 3.3-3.6;
- the mineralizer to be formulated is fluoride, preferably calcium fluoride, and the calcium fluoride is added in an amount of 0.5-7% by mass, preferably 1-3%, of the dry tungsten mineral raw material.
- the mass percentage is not particularly limited, and is preferably not more than 200 ⁇ m, more preferably not more than 100 ⁇ m, more preferably not more than 40 ⁇ m; the raw material baking temperature is not lower than 500 ° C, preferably the raw material baking temperature is 800.
- the calcination time is not particularly limited, and the calcination time is required to be extended, so that the tungsten in the raw meal is sufficiently converted into Ca 3 WO 6 and/or Ca 2 FeWO 6 and/or Or Ca 2 MnWO 6 , preferably calcined for 0.5-8.0 h, more preferably 1.0-3.0 h, more preferably calcined at 850-950 ° C for 2.0 h.
- the baking atmosphere is not particularly limited, and is preferably a neutral or oxidizing atmosphere; for the wolframite, black and white tungsten mixed ore and/or tungsten fine mud raw material, the baking atmosphere is a neutral or reducing atmosphere, preferably It is a neutral atmosphere.
- a mixture containing Ca 3 WO 6 and/or Ca 2 FeWO 6 and/or Ca 2 MnWO 6 is added to an ammonium salt solution system, and leached under closed conditions. After the leaching is completed, the leaching slurry is separated and washed to obtain Ammonium tungstate solution.
- the Ca 3 WO 6 and/or Ca 2 FeWO 6 and/or Ca 2 MnWO 6 may be a purely synthetic compound, or may be a Ca 3 WO 6 and/or obtained after processing the tungsten mineral raw material. a mixture of Ca 2 FeWO 6 and/or Ca 2 MnWO 6 (clinker); a mixture of Ca 3 WO 6 and/or Ca 2 FeWO 6 and/or Ca 2 MnWO 6 having a particle size of not more than 200 ⁇ m, preferably less than 45 ⁇ m;
- the ammonium salt solution system may be ammonium carbonate-ammonium hydrogencarbonate-ammonium tungstate system, ammonium carbonate-ammonium tungstate-CO 2 system, ammonium carbonate-ammonia water-tungstate ammonium system, ammonium carbonate-ammonia system, carbonic acid Ammonium system, ammonium carbonate-ammonium bicarbonate system, ammonium carbonate-ammonia-CO 2 system, ammonium carbonate-ammonia-tungstate
- ammonium carbonate system ammonium carbonate-ammonium hydrogencarbonate system, ammonium carbonate-ammonia system, ammonium carbonate-ammonium hydrogencarbonate-ammonium tungstate system, ammonium carbonate-ammonia-tungstate ammonium system and ammonium carbonate-tungstate ammonium
- the absolute pressure of the leaching system is not particularly limited; using ammonium carbonate-CO 2 system, ammonium carbonate-ammonium hydrogencarbonate-CO 2 system Ammonium carbonate-ammonia-CO 2 system, ammonium carbonate-ammonium tungstate-CO 2 system, ammonium carbonate-ammonia-tungstate-CO 2 system and ammonium carbonate-ammonium hydrogencarbonate-ammonium tungstate-CO 2 system leaching Ca 3 WO 6 and/or Ca 2 FeWO 6 and/or Ca 2 MnWO 6 , CO 2 is introduced
- the ammonium tungstate concentration is also not particularly limited as long as Ca 3 WO 6 and/or Ca 2 FeWO 6 and/or Ca 2 MnWO are satisfied. After the tungsten in 6 is sufficiently leached, the concentration of ammonium tungstate in the resulting solution does not exceed its solubility in the system.
- the amount of ammonium hydrogen added is not particularly limited, and is preferably not less than 1.0 times the theoretical amount, and more preferably 1.1 to 1.4 times the theoretical amount.
- the amount of ammonia added is not particularly
- the preferred leaching initial system has a mass percentage of NH3 of from 0 to 28%, more preferably from 5 to 20%, still more preferably from 5 to 10%.
- the pH of the leaching system is controlled to be not less than 8.0.
- the leaching temperature is not lower than 5 ° C, preferably 10-80 ° C, more preferably 20-70 ° C, more preferably 30-50 ° C; the leaching time is not particularly limited as long as Ca 3 WO 6 and/or Ca 2 can be made.
- the tungsten in FeWO 6 and/or Ca 2 MnWO 6 may be sufficiently leached, preferably from 0.5 to 8.0 h, and more preferably from 2-3 to hr.
- the leaching system has an initial liquid to solid ratio of not less than 1:1 mL/g, preferably 10:1 to 4:1 mL/g.
- the final liquid to solid ratio of the leaching system can be reduced by means of multi-stage feeding, preferably by two-stage feeding, to control the liquid-solid ratio of the final leaching system from 3:1 to 4:1 mL/g.
- the ammonium carbonate solution may also be partially replaced by ammonium bicarbonate solution and ammonia water, or ammonia water and CO 2 .
- (NH 4 ) 2 WO 4 When the concentration of (NH 4 ) 2 WO 4 in the solution is high, especially in the presence of a large amount of NH 4 OH, (NH 4 ) 2 WO 4 will react twice with the highly active CaCO 3 formed during the leaching process. CaWO 4 which is difficult to be leached by the ammonium carbonate solution is generated, resulting in loss of tungsten.
- the main reaction may be:
- the reaction (2) is easier to carry out, and in general, the reaction (1) is difficult to carry out, but the new CaCO 3 activity is high during the leaching of Ca 3 WO 6 , and the reaction (1) is possible, and with the leaching process
- the concentration of NH 4 OH and (NH 4 ) 2 WO 4 is continuously increased, and the reaction (1) and the reaction (2) are strengthened, eventually resulting in an increase in the loss of tungsten at a higher concentration of (NH 4 ) 2 WO 4 . Therefore, CO 2 is introduced into the closed leaching system to rapidly neutralize the NH 4 OH in the solution, thereby suppressing the reaction (1); at the same time, by adding the CaCO 3 seed crystal, the nascent CaCO 3 is rapidly grown on the surface of the seed crystal. , reducing its activity and further inhibiting the progress of the reaction (1). It is thus expected to simultaneously obtain a high concentration of (NH 4 ) 2 WO 4 solution and a high tungsten leaching rate.
- the crude ammonium tungstate solution is purified and removed, and the method for purifying and removing impurities is not particularly limited as long as the solution is P, As, Si, Mo, S, Sn, Sb, Ca, Mg,
- the content of impurities such as K and Na can meet the quality requirements of the qualified APT products.
- impurities in the ammonium tungstate solution may be removed by a precipitation method, thereby preparing an ammonium tungstate refining liquid.
- the ATP can be obtained by an evaporation crystallization method using the ammonium tungstate refined solution, and the conditions for the evaporation crystallization are not particularly limited.
- the ammonium tungstate solution is evaporated to a pH of 6.5 at 95 ° C. After solid-liquid separation and product washing, the purity of the obtained APT product meets the standard of GB/T 10116-2007. .
- Example 1 According to the CaO/WO 3 molecular ratio of 3.3, a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) and clinker leaching residue (main component is CaCO 3 ) And the mineralizer calcium fluoride is ground and mixed to obtain the raw material.
- the calcium fluoride is added in an amount of 5.2% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 40 ⁇ m, and then, in the baking furnace In the air atmosphere, calcination was carried out at 800 ° C for 2.0 h to obtain clinker. After the clinker was cooled to room temperature, it was ground with a vibrating mill, and the clinker size was ⁇ 45 ⁇ m.
- Example 2 According to the (CaO+FeO)/WO 3 molecular ratio of 4.5, a black and white tungsten mixed ore (WO 3 mass percentage of 63.75%, Fe mass percentage of 5.90%) and clinker leaching residue were carried out. After grinding and mixing, the raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then, in a shaft furnace, calcined at 950 ° C for 3.0 h under a weak reducing atmosphere to obtain clinker. After the clinker was cooled to room temperature, it was ground with a ball mill, and the clinker size was ⁇ 45 ⁇ m.
- Example 3 According to (CaO + FeO + MnO) / WO 3 molecular ratio of 3.4, a certain black tungsten ore (WO 3 mass percentage of 62.40%, Fe mass percentage of 14.08%, Mn mass percentage) It is 2.25%) and is chopped and mixed with clinker leaching residue and calcium fluoride to obtain raw material. The amount of calcium fluoride added is 7% (mass percentage) of dry tungsten mineral raw material, and the raw material particle size is ⁇ 40 ⁇ m.
- the leaching equipment is selected by ball milling leaching A saturated solution of ammonium carbonate was built in, and ammonium hydrogencarbonate was added at 1.0 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 80 ° C for 4 hours. After the reaction was completed, the leached slurry was vacuum filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 97.13%.
- the crude ammonium tungstate solution is purified and decontaminated, and the solution is precipitated by evaporation crystallization to form APT, and at the same time, ammonia gas and carbon dioxide gas are obtained, and the crystallized slurry is subjected to liquid-solid separation to obtain a crystallization mother liquid and a solid phase, and the solid phase is passed through water.
- the APT product is obtained, and the APT product meets the national zero-grade product standard; the obtained ammonia gas is returned to the leaching equipment together with the carbon dioxide, and the clinker is circulated after the loss of the lost ammonium carbonate.
- Example 4 According to the (CaO+FeO)/WO 3 molecular ratio of 3.0, a certain black tungsten ore (WO 3 mass percentage of 42.17%, Fe mass percentage of 11.34%) and clinker leaching residue and fluorine The calcium is subjected to grinding and mixing to obtain a raw material.
- the amount of calcium fluoride added is 1.5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then, in the baking furnace, the weak reducing atmosphere Next, calcination at 850 ° C for 5.0 h, clinker is obtained, clinker is cooled to room temperature, finely ground with agitating mill, clinker size ⁇ 45 ⁇ m; leaching equipment selects ball mill dissolver, built-in saturated solution of ammonium carbonate, and according to the theoretical amount of 1.1 The ammonium bicarbonate was added in multiple portions; the clinker was placed in a leaching apparatus and reacted at 40 ° C for 4 h.
- Example 5 Grinding a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%), clinker leaching slag and calcium fluoride according to a CaO/WO 3 molecular ratio of 6.0 After fine mixing, the raw material is obtained.
- the calcium fluoride is added in an amount of 3% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 870 ° C for 4 hours to obtain a ripe
- the leaching equipment is selected with a stirring leaching tank, a saturated solution of ammonium carbonate is built in, and ammonium hydrogencarbonate is added at 1.3 times the theoretical amount;
- the clinker is placed in the leaching equipment, and ammonia water is added (so that the mass percentage of NH 3 in the leaching solution is 5%) and sealed, and then carbon dioxide gas is introduced to control the absolute pressure of the leaching system to 2 atm, and react at 30 ° C for 5 hours. . After the reaction was completed, the slurry was leached and the filter cake was washed three times with
- Example 6 Grinding a scheelite (WO 3 mass percent content of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to (CaO+FeO)/WO 3 molecular ratio of 7 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 1000 ° C for 7 hours to obtain clinker.
- the leaching equipment selects the ball mill leaching device, the built-in ammonium carbonate solution, the ammonium carbonate concentration is 35g-(NH 4 ) 2 CO 3 /100g-H 2 O, and the ammonium bicarbonate is added according to the theoretical amount of 1.3 times; the clinker is placed Into the leaching equipment, react at 40 ° C for 9 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 98.99%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 7 After a molar ratio of CaO/WO 3 is 7, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed. The raw material is obtained, the raw material particle size is ⁇ 40 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 950 ° C for 5 hours to obtain clinker.
- the leaching equipment Select a leaching tank with agitation, a mixture of saturated ammonium carbonate and ammonium tungstate containing 20 g / L WO 3 , and add ammonium bicarbonate 1.4 times the theoretical amount; put the clinker into the leaching equipment, and add ammonia water (to make leaching)
- the NH 3 content in the solution was 9.5% by mass and sealed, and then carbon dioxide gas was introduced to control the absolute pressure of the leaching system to 3 atm and react at 20 ° C for 6 h.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten was 99.01%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 8 According to the CaO/WO 3 molecular ratio of 8, a tungsten fine mud (WO 3 mass percentage of 16.22%) and clinker leaching residue were ground and mixed to obtain a raw meal, and the raw material particle size was ⁇ 40 ⁇ m. Then, calcined in a reducing atmosphere of the calciner at 940 ° C for 3 hours to obtain clinker, and the clinker is cooled to room temperature; the leaching device selects a leaching tank with stirring, and a mixture of saturated ammonium carbonate and ammonium tungstate containing 120 g/L of WO 3 is mixed.
- Example 9 Grinding a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 1.5 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 965 ° C for 1.5 hours to obtain clinker. After the clinker is cooled to room temperature, it is ground by a roller mill, and the clinker particle size is obtained.
- the leaching equipment selects the ball mill leaching device, the built-in ammonium carbonate solution, the ammonium carbonate concentration is 67g-(NH 4 ) 2 CO 3 /100g-H 2 O, and the ammonium bicarbonate is added according to the theoretical amount of 1.4 times; It was placed in a leaching apparatus and reacted at 18 ° C for 6.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 29.30%.
- Example 10 According to the (CaO+FeO)/WO 3 molecular ratio of 1.2, a black and white tungsten mixed ore (WO 3 mass percentage of 43.20%, Fe mass percentage of 7.18%) and clinker leaching residue were carried out. After grinding and mixing, the raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the roaster at 500 ° C for 3 hours to obtain clinker.
- the leaching equipment selects the ball mill leaching device, the built-in ammonium carbonate solution, the ammonium carbonate concentration is 50g-(NH 4 ) 2 CO 3 /100g-H 2 O, and the ammonium bicarbonate is added according to the theoretical amount of 1.25 times;
- the leaching equipment react at 28 ° C for 3.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 9.76%.
- Example 11 After a molar ratio of CaO/WO 3 is 9, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed. The raw material is obtained, the raw material particle size is ⁇ 200 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 950 ° C for 4 hours to obtain clinker.
- the leaching equipment Select the leaching tank with stirring, built a saturated solution of ammonium carbonate, and add ammonium bicarbonate according to the theoretical amount of 1.1 times; put the clinker into the leaching equipment and add ammonia water (so that the mass percentage of NH 3 in the leaching solution is 10 %) and sealed, reacted at 27 ° C for 4.5 h. After the reaction was completed, the slurry was leached and filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 89.05%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 12 After a molar ratio of CaO/WO 3 is 2.3, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed. The raw material is obtained, and the calcium fluoride is added in an amount of 1% by mass of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 100 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 845 ° C for 2.5 hours to obtain clinker and cooked.
- a molar ratio of CaO/WO 3 is 2.3
- a scheelite WO 3 mass percent content is 49.53%
- Fe mass percentage is 0.43%
- the leaching equipment selects the leaching tank with stirring, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.2 times; the clinker is put into the leaching
- the equipment was simultaneously added with ammonia (the mass percentage of NH 3 in the leaching solution was 5.9%) and sealed, and then carbon dioxide gas was introduced to control the absolute pressure of the leaching system to 2.5 atm and the reaction at 27 ° C for 4.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten is 73.65%. Then, similar to Example 3 but supplemented with ammonia water and ammonium hydrogencarbonate.
- Example 13 After a molar ratio of CaO/WO 3 of 3.6, a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) was ground and mixed with clinker leaching residue. The raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 870 ° C for 1 h to obtain clinker.
- a scheelite WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%
- the leaching equipment Select the leaching tank with stirring, built a saturated solution of ammonium carbonate, and add ammonium bicarbonate at 1.4 times the theoretical amount; put the clinker into the leaching equipment and add ammonia water (so that the mass percentage of NH 3 in the leaching solution is 20 %) and sealed, reacted at 32 ° C for 3.8 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 96.15%. Then, similar to Example 3 but supplemented with ammonium bicarbonate.
- Example 14 Grinding a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.5 After fine mixing, the raw material is obtained. The calcium fluoride is added in an amount of 0.5% by mass of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 50 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 920 ° C for 2 hours to obtain a cooked product.
- the clinker size is ⁇ 45 ⁇ m; the leaching equipment is selected to stir the leaching device, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.2 times; Place in a leaching apparatus and react at 38 ° C for 2 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed twice with pure water. The leaching rate of tungsten was 98.22%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 15 Grinding a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 3.4 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 960 ° C for 2 hours to obtain clinker.
- the clinker After the clinker is cooled to room temperature, it is ground by a rod mill, and the clinker size is ⁇ 200 ⁇ m; the leaching equipment was selected from a ball mill leacher, a saturated solution of ammonium carbonate was built in, and ammonium bicarbonate was added at 1.2 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 38 ° C for 5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed twice with pure water. The leaching rate of tungsten is 98.35%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 16 Grinding a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.1 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 61 ⁇ m, and then calcined in the oxidizing atmosphere of the roaster at 970 ° C for 2 hours to obtain clinker, the clinker is cooled to room temperature, and then ground with a ball mill, the clinker particle size is ⁇ 74 ⁇ m; The leaching equipment was selected from a ball mill leaching device, a saturated solution of ammonium carbonate was built in, and ammonium hydrogencarbonate was added at 1.4 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 55 ° C for 4 hours.
- a scheelite WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%
- clinker leaching residue according to a (CaO
- the leaching slurry was suction filtered, and the filter cake was washed twice with pure water.
- the leaching rate of tungsten was 97.31%.
- the APT product meets the national 0 standard product standard.
- Example 17 After a molar ratio of CaO/WO 3 is 6.5, a scheelite (WO 3 mass percent content is 52.33%, Fe mass percentage is 2.04%) and the clinker leaching residue is ground and mixed. The raw material is obtained, the raw material particle size is ⁇ 53 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 990 ° C for 0.5 h to obtain clinker.
- the clinker After the clinker is cooled to room temperature, it is ground by a planetary mill, and the clinker particle size is ⁇ 45 ⁇ m; leaching The equipment was selected to stir the leaching device, a saturated solution of ammonium carbonate was built in, and ammonium bicarbonate was added at 1.5 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 62 ° C for 2 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed 5 times with pure water. The leaching rate of tungsten is 96.78%. Then, similar to Example 3 but supplemented with ammonium carbonate and ammonia, the APT product meets the national 0 grade standard requirements.
- Example 18 Grinding a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.7 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 74 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 980 ° C for 2 hours to obtain clinker. After the clinker is cooled to room temperature, it is ground by a high-pressure disc mill, and the clinker particle size is obtained.
- the leaching equipment selects the stirring leaching device, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.6 times; the clinker is placed in the leaching equipment and reacted at 75 ° C for 3.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed twice with pure water. The leaching rate of tungsten was 97.01%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 19 After a molar ratio of CaO/WO 3 of 3.8, a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) was ground and mixed with clinker leaching residue. The raw material is obtained, and the calcium fluoride is added in an amount of 0.5% by mass of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 40 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 880 ° C for 1 hour to obtain clinker and clinker.
- a scheelite WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%
- the leaching equipment selects the leaching tank with stirring, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.4 times; the clinker is put into the leaching equipment
- ammonia water (the mass percentage of NH 3 in the leaching solution was 8.2%) was added and sealed, and then carbon dioxide gas was introduced to control the absolute pressure of the leaching system to 3 atm, and the reaction was carried out at 32 ° C for 3.8 h.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten was 98.15%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 20 After a molar ratio of CaO/WO 3 is 3.8, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed. The raw material is obtained, and the calcium fluoride is added in an amount of 5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 30 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 860 ° C for 1 h to obtain clinker and clinker.
- the leaching equipment selects the leaching tank with stirring, and the mixed solution of saturated ammonium carbonate and ammonium tungstate containing 60g/L WO 3 is built in; the clinker is placed
- the leaching equipment was simultaneously added with ammonia water (the mass percentage of NH 3 in the leaching solution was 15%) and sealed, and then carbon dioxide gas was introduced to control the absolute pressure of the leaching system to 1.2 atm, and reacted at 35 ° C for 6 hours. After the reaction was completed, the slurry was leached and filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 98.03%. Then, similar to Example 3 but supplemented with ammonia, CO 2 and ammonium carbonate.
- Example 21 After a molar ratio of CaO/WO 3 of 2.0, a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) was ground and mixed with clinker leaching residue. The raw material is obtained, the raw material particle size is ⁇ 36 ⁇ m, and then calcined in a reducing atmosphere of the calciner at 880 ° C for 1 h to obtain clinker.
- a scheelite WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%
- the leaching equipment Select a leaching tank with stirring, a saturated solution of ammonium carbonate, and add ammonium bicarbonate at 1.4 times the theoretical amount; put the clinker into the leaching equipment and add ammonia water (so that the mass percentage of NH 3 in the leaching solution is 10.0) %) and sealed, then carbon dioxide gas was introduced, the absolute pressure of the leaching system was controlled to 1.5 atm, and the reaction was carried out at 32 ° C for 3.8 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten is 42.75%. Then, similar to Example 3 but supplemented with ammonium bicarbonate, ammonia and CO 2 .
- Example 22 After a molar ratio of CaO/WO 3 of 1.8, a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) was ground and mixed with clinker leaching residue. The raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 880 ° C for 1 h to obtain clinker.
- a scheelite WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%
- the leaching equipment selection belt Stirred leaching tank, built-in saturated solution of ammonium carbonate, and added ammonium bicarbonate at 1.4 times the theoretical amount; put the clinker into the leaching equipment, and add ammonia water (so that the mass percentage of NH3 in the leaching solution is 7.4%) Sealed, then, carbon dioxide gas was introduced, the absolute pressure of the leaching system was controlled to be 1.9 atm, and the reaction was carried out at 32 ° C for 3.8 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten is 38.35%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 23 Grinding a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 1.5 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 33 ⁇ m, and then calcined in a neutral atmosphere of the roaster at 965 ° C for 5 hours to obtain clinker.
- the leaching equipment selects the ball mill leaching device, the built-in ammonium carbonate solution, the ammonium carbonate concentration is 80g-(NH 4 ) 2 CO 3 /100g-H 2 O, and the ammonium bicarbonate is added according to the theoretical amount of 1.4 times; the clinker is placed
- the equipment was leached and reacted at 20 ° C for 6.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 22.96%. Then, similar to Example 3.
- Example 24 According to the (CaO+FeO)/WO 3 molecular ratio of 2.9, a black and white tungsten mixed ore (WO 3 mass percentage of 43.20%, Fe mass percentage of 7.18%) and clinker leaching residue were carried out. After grinding and mixing, the raw material is obtained. The calcium fluoride is added in an amount of 2% by mass of the dry tungsten mineral raw material, the raw material particle size is ⁇ 30 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 850 ° C for 3 hours.
- Example 25 After a molar ratio of CaO/WO 3 is 4, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed.
- the raw material is obtained, the raw material particle size is ⁇ 28 ⁇ m, and then calcined in a roasting furnace oxidizing atmosphere at 950 ° C for 4 h to obtain clinker, the clinker is cooled to room temperature, and then ground with a ball mill, the clinker particle size is ⁇ 45 ⁇ m; the leaching equipment selection belt
- the stirred leaching tank is filled with a saturated solution of ammonium carbonate; the clinker is placed in a leaching apparatus, and ammonia water is added (the mass percentage of NH 3 in the leaching solution is 20%) and sealed, and reacted at 27 ° C for 4.5 hours. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water
- Example 26 After a molar ratio of CaO/WO 3 is 2.3, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed. The raw material is obtained, and the calcium fluoride is added in an amount of 4.5% by mass of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 41 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 845 ° C for 2.5 hours to obtain clinker and cooked.
- a molar ratio of CaO/WO 3 is 2.3
- a scheelite WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%
- the clinker leaching residue is ground and mixed.
- the raw material is obtained, and the calcium fluoride is added in an amount of 4.5% by mass of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 41 ⁇ m, and then calcined in a neutral atmosphere of the baking
- the mixture is ground by a ball mill, the clinker size is ⁇ 83 ⁇ m; the leaching equipment selects the ball mill leacher, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.2 times; the clinker is placed in the leaching equipment.
- ammonia water (having a mass percentage of NH3 in the leaching solution of 9.8%) was added and sealed, and reacted at 37 ° C for 4.5 hours.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten is 68.65%.
- Example 3 Similar to Example 3 but supplemented with ammonium carbonate, ammonia and CO 2 .
- Example 27 Grinding a scheelite (WO 3 mass percent of 52.27%, Fe mass percentage of 5.86%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.8 After fine mixing, the raw material is obtained.
- the calcium fluoride is added in an amount of 2.5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 61 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 870 ° C for 1 h to obtain a cooked
- the clinker is cooled to room temperature, it is ground with a rod mill, the clinker size is ⁇ 45 ⁇ m;
- the leaching equipment is selected with a stirring leaching tank, a saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.4 times;
- the clinker was placed in a leaching apparatus and reacted at 32 ° C for 8.0 h.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten was 97.10%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 28 a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and rhombohedral and limestone according to a (CaO + FeO + MnO) / WO 3 molecular ratio of 4.5
- the raw material is obtained, the raw material particle size is ⁇ 14 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 920 ° C for 2 h to obtain clinker. After the clinker is cooled to room temperature, it is ground by a vibration mill, and the clinker particle size is obtained.
- the leaching equipment selects the ball mill leaching device, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.2 times; the clinker is placed in the leaching equipment and reacted at 43 ° C for 5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed twice with pure water. The leaching rate of tungsten was 98.42%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 29 Grinding a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.9 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 42 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 960°C for 2h to obtain clinker. After the clinker is cooled to room temperature, it is finely ground by a planetary mill, and the clinker size is ⁇ 45 ⁇ m.
- the leaching equipment was selected as a stirring leaching device, a saturated solution of ammonium carbonate was built in, and ammonium hydrogencarbonate was added at 1.2 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 38 ° C for 5 hours. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed twice with pure water. The leaching rate of tungsten is 97.35%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 30 According to the (CaO+MnO)/WO 3 molecular ratio of 4.6, a scheelite (WO 3 mass percent content of 60.94%) was finely mixed with rhodochrosite and clinker leaching residue to obtain a raw
- the raw material has a particle size of ⁇ 44 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 980 ° C for 1.5 h to obtain clinker. After the clinker is cooled to room temperature, it is ground with a stirring mill, and the clinker size is ⁇ 45 ⁇ m; the leaching equipment is selected to be stirred.
- the leaching device was filled with a saturated solution of ammonium carbonate, and ammonium hydrogencarbonate was added at 1.5 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 50 ° C for 4 hours. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed 4 times with pure water. The leaching rate of tungsten was 97.99%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 31 According to the CaO/WO 3 molecular ratio of 4.3, a scheelite (WO 3 mass percentage of 60.94%) and clinker leaching residue were ground and mixed to obtain a raw meal, and the raw material particle size was ⁇ 48 ⁇ m. Then, calcined in a neutral atmosphere of the calciner at 970 ° C for 2 h to obtain clinker, the clinker is cooled to room temperature, and then ground with a rod mill, the clinker size is ⁇ 45 ⁇ m; the leaching equipment is selected to stir the leaching device, and the built-in ammonium carbonate is saturated.
- the solution was added to ammonium bicarbonate at 1.2 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 55 ° C for 4 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed with pure water. The leaching rate of tungsten was 97.74%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 32 Grinding a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.9 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 38 ⁇ m, and then calcined in the oxidizing atmosphere of the baking furnace at 990 ° C for 1 hour to obtain clinker.
- the clinker After the clinker is cooled to room temperature, it is ground by a ball mill, and the clinker size is ⁇ 45 ⁇ m; leaching The equipment was selected to stir the leaching device, a saturated solution of ammonium carbonate was built in, and ammonium bicarbonate was added at 1.5 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 62 ° C for 4 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed 5 times with pure water. The leaching rate of tungsten was 97.78%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 33 According to the CaO/WO 3 molecular ratio of 5.1, a scheelite (WO 3 mass percentage of 60.94%) and the clinker leaching residue were ground and mixed to obtain a raw meal, and the raw material particle size was ⁇ 63 ⁇ m. Then, calcined in a neutral atmosphere of the calciner at 980 ° C for 2 h to obtain clinker, the clinker is cooled to room temperature, and then ground with a stirring mill, the clinker size is ⁇ 45 ⁇ m; the leaching equipment is selected to stir the leaching device, and the saturated ammonium carbonate solution is built in.
- the APT product meets the national 0 standard product standard.
- Example 34 Leaching a scheelite (WO 3 mass percent content of 49.53%, Fe mass percentage of 0.43%) with rhombohedral or clinker according to a (CaO + MnO) / WO 3 molecular ratio of 5.1
- the slag is ground and mixed to obtain a raw material.
- the calcium fluoride is added in an amount of 6.0% by mass of the dry tungsten mineral raw material, the raw material particle size is ⁇ 36 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 880 ° C for 1 hour.
- the clinker After obtaining the clinker, the clinker is cooled to room temperature, finely ground with a stirring mill, and the clinker size is ⁇ 45 ⁇ m; the leaching equipment is selected with a stirring leaching tank, a saturated solution of ammonium carbonate is built in, and ammonium hydrogencarbonate is added at 1.5 times the theoretical amount.
- the clinker was placed in a leaching apparatus while adding ammonia water (so that the mass percentage of NH 3 in the leaching solution was 5.0%) and sealed, and reacted at 32 ° C for 3.8 h. After the reaction was completed, the slurry was leached and filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 98.15%. Then, similar to Example 3, but supplemented with ammonium carbonate, ammonium hydrogencarbonate, aqueous ammonia and CO 2 .
- Example 35 Leaching a scheelite (WO 3 mass percent of 49.53%, Fe mass percentage of 0.43%) with rhombohedral or clinker according to a (CaO + MnO) / WO 3 molecular ratio of 5.1 After the slag is ground and mixed, the raw material is obtained, the raw material particle size is ⁇ 36 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 880 ° C for 1 hour to obtain clinker.
- the leaching equipment selects a leaching tank with stirring, a saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added 1.5 times the theoretical amount; the clinker is placed in the leaching equipment, and ammonia water is added at the same time (to make the NH 3 in the leaching solution)
- the mass percentage was 5.0%) and sealed, and reacted at 32 ° C for 3.8 h.
- the slurry was leached and filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten was 86.23%.
- Example 3 Similar to Example 3, but supplemented with ammonium carbonate, ammonium hydrogencarbonate, aqueous ammonia and CO 2 .
- Example 36 After a molar ratio of CaO/WO 3 is 2.5, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed. The raw material is obtained, the calcium fluoride is added in an amount of 4.5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 37 ⁇ m, and then calcined in a reducing atmosphere of the calciner at 880 ° C for 1 h to obtain clinker and clinker.
- the leaching equipment selects the leaching tank with stirring, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.15 times; the clinker is put into the leaching
- the equipment was simultaneously added with ammonia (the mass percentage of NH 3 in the leaching solution was 4.1%) and sealed, and then carbon dioxide gas was introduced to control the absolute pressure of the leaching system to be 1.3 atm, and reacted at 32 ° C for 9 hours.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten is 74.75%.
- Example 3 Similar to Example 3 but supplemented with ammonium bicarbonate, ammonia and CO 2 .
- Example 37 According to the CaO/WO 3 molecular ratio of 2.2, a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) was ground and mixed with limestone to obtain a raw meal. Calcium fluoride is added in an amount of 1.5% by mass of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 24 ⁇ m, and then calcined in a reducing atmosphere of the calciner at 880 ° C for 3 hours to obtain clinker, and the clinker is cooled to room temperature.
- a scheelite WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%
- the leaching equipment selects a ball mill leacher, and a saturated solution of ammonium carbonate is built therein; the clinker is placed in a leaching apparatus and reacted at 32 ° C for 8.0 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 55.45%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 38 a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and siderite and clinker according to a (CaO+FeO)/WO 3 molecular ratio of 10
- the leaching residue is ground and mixed to obtain a raw meal, and the raw material particle size is ⁇ 38 ⁇ m. Then, it is calcined in a neutral atmosphere of the baking furnace at 950 ° C for 1 hour to obtain clinker. After the clinker is cooled to room temperature, it is finely ground by vibration grinding.
- the particle size is ⁇ 45 ⁇ m; the leaching equipment selects the ball mill leacher, the built-in ammonium carbonate solution, the ammonium carbonate concentration is 58g-(NH 4 ) 2 CO 3 /100g-H 2 O, and the ammonium hydrogencarbonate is added according to the theoretical amount 1.3 times;
- the clinker was placed in a leaching apparatus and reacted at 40 ° C for 9 h. After the reaction was completed, the slurry was leached and filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten was 96.93%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 39 After a molar ratio of CaO/WO 3 is 5.1, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed. The raw material is obtained, and the calcium fluoride is added in an amount of 1.0% by mass of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 33 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 895 ° C for 8 hours to obtain clinker and clinker.
- the leaching equipment selects the leaching tank with stirring, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added at 1.9 times the theoretical amount; the clinker is placed in the leaching
- the equipment was reacted at 20 ° C for 6 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 95.01%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 40 According to the CaO/WO 3 molecular ratio of 3.9, a tungsten fine mud (WO 3 mass percentage of 16.22%) was finely mixed with limestone to obtain a raw meal, the raw material particle size was ⁇ 40 ⁇ m, and then, After calcination in a reducing atmosphere of the calciner at 940 ° C for 3 h, clinker is obtained, and the clinker is cooled to room temperature, and then ground with a ball mill, the clinker size is ⁇ 45 ⁇ m; the leaching equipment is selected with a stirring leaching tank, and a saturated solution of ammonium carbonate is built; The clinker was placed in a leaching apparatus while adding ammonia water (the mass percentage of NH 3 in the leaching solution was 12%) and sealed, and reacted at 50 ° C for 4 hours.
- a tungsten fine mud WO 3 mass percentage of 16.22%) was finely mixed with limestone to obtain a raw meal, the raw material particle size was ⁇ 40 ⁇ m,
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten was 92.31%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 41 Grinding and mixing a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) with limestone according to a (CaO+FeO)/WO 3 molecular ratio of 6.5 After the raw material is obtained, the calcium fluoride is added in an amount of 0.7% by mass of the dry tungsten mineral raw material, the raw material particle size is ⁇ 30 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 965 ° C for 1.5 h to obtain a clinker.
- a scheelite WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%
- the clinker size is ⁇ 74 ⁇ m; the leaching equipment selects the ball mill leacher, and the ammonium carbonate solution is built in, the ammonium carbonate concentration is 67g-(NH 4 ) 2 CO 3 /100g-H 2 O, And ammonium bicarbonate was added at 1.4 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 10 ° C for 20.0 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten is 91.96%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 42 According to the (CaO+FeO)/WO 3 molecular ratio of 3.6, a black and white tungsten mixed ore (WO 3 mass percentage of 43.20%, Fe mass percentage of 7.18%) and clinker leaching residue were carried out. After grinding and mixing, the raw material is obtained. The calcium fluoride is added in an amount of 2.6% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 25 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 850 ° C for 3 hours.
- Example 43 After a molar ratio of CaO/WO 3 of 10, a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) was ground and mixed with clinker leaching residue. The raw material is obtained, the raw material particle size is ⁇ 28 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 845 ° C for 4 hours to obtain clinker. After the clinker is cooled to room temperature, it is ground by a vibration mill, and the clinker size is ⁇ 74 ⁇ m; the leaching equipment is selected.
- the leaching tank with stirring is filled with a saturated solution of ammonium carbonate; the clinker is placed in a leaching apparatus, ammonia water is added (the mass percentage of NH 3 in the leaching solution is 28%), and it is sealed, and reacted at 27 ° C for 4.5 hours. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 96.01%. Then, similar to Example 3 but supplemented with ammonium carbonate, ammonia and CO 2 .
- Example 44 After a molar ratio of CaO/WO 3 of 3.5, a scheelite (WO 3 mass percent content of 49.53%, Fe mass percentage of 0.43%) was ground and mixed with clinker leaching residue. The raw material is obtained, and the calcium fluoride is added in an amount of 5.5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 40 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 845 ° C for 10 hours to obtain clinker and clinker.
- a scheelite WO 3 mass percent content of 49.53%, Fe mass percentage of 0.43%
- the clinker size is ⁇ 150 ⁇ m; the leaching equipment selects the ball mill leacher, and the saturated solution of ammonium carbonate is built in; the clinker is put into the leaching equipment, and ammonia water is added at the same time (so that NH 3 is leached in the solution) The mass percentage was 7.5%) and sealed, and reacted at 27 ° C for 4.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 98.49%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 45 After a molar ratio of CaO/WO 3 of 4.5, a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) was ground and mixed with clinker leaching residue. The raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 1050 ° C for 6 hours to obtain clinker.
- a scheelite WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%
- the leaching equipment Select the leaching tank with stirring, built-in saturated solution of ammonium carbonate; put the clinker into the leaching equipment, add ammonia water (so that the mass percentage of NH 3 in the leaching solution is 9.1%) and seal it, and react at 380 ° C for 3.8 h. .
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 97.15%.
- Example 3 similar to Example 3 but supplemented with ammonium bicarbonate, ammonia and CO 2 .
- Example 46 Grinding a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.5 After fine mixing, the raw material is obtained. The amount of calcium fluoride added is 6% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 995 ° C for 0.5 h.
- Example 47 Grinding a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 5.5 After fine mixing, the raw material is obtained.
- the amount of calcium fluoride added is 2% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a reducing atmosphere of the calciner at 960 ° C for 2 h to obtain a cooked
- the clinker size is ⁇ 20 ⁇ m
- the leaching equipment is selected to stir the leaching device, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.2 times; It was placed in a leaching apparatus and reacted at 38 ° C for 5 h.
- the leaching slurry was suction filtered, and the filter cake was washed twice with pure water.
- the leaching rate of tungsten was 98.16%.
- the APT product meets the national 0 standard product standard.
- Example 48 Grinding a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.2 After fine mixing, the raw material is obtained. The amount of calcium fluoride added is 3.5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 850 ° C for 0.5 h.
- Example 49 Grinding a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.1 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 53 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 930 ° C for 8 hours to obtain clinker. After the clinker is cooled to room temperature, it is ground by a hanging roller mill, and the clinker particle size is obtained.
- the leaching equipment is selected to stir the leaching device, a saturated solution of ammonium carbonate is built in, and ammonium hydrogencarbonate is added at 1.1 times the theoretical amount; the clinker is placed in a leaching apparatus and reacted at 25 ° C for 4 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed twice with pure water. The leaching rate of tungsten was 94.22%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 50 According to the CaO/WO 3 molecular ratio of 5.6, a scheelite (WO 3 mass percentage of 60.94%) and clinker leaching residue were ground and mixed to obtain a raw material, and calcium fluoride was added. The amount is 2.5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 53 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 910 ° C for 1 h to obtain clinker. After the clinker is cooled to room temperature, it is ground with a ball mill.
- the clinker size is ⁇ 45 ⁇ m; the leaching equipment selects the stirring leaching device, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount 1.5 times; the clinker is placed in the leaching equipment and reacted at 62 ° C for 4 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed 5 times with pure water. The leaching rate of tungsten was 98.78%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 51 Grinding a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.7 After fine mixing, the raw material is obtained.
- the calcium fluoride is added in an amount of 2.8% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 74 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 900 ° C for 2 hours to obtain a cooked
- the clinker size is ⁇ 45 ⁇ m;
- the leaching equipment is selected to stir the leaching device, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.6 times; the clinker is placed The leaching equipment was reacted at 75 ° C for 1.5 h.
- the leaching slurry was suction filtered, and the filter cake was washed twice with pure water.
- the leaching rate of tungsten was 95.01%.
- the APT product meets the national 0 standard product standard.
- Example 52 After a molar ratio of CaO/WO 3 is 3.8, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed.
- the raw material is obtained, the calcium fluoride is added in an amount of 3.3% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 880 ° C for 1 h to obtain clinker and clinker.
- the leaching equipment selects the leaching tank with stirring, and the saturated solution of ammonium carbonate is built in; the clinker is put into the leaching equipment, and ammonia water is added at the same time (the NH 3 in the leaching solution is made )
- the mass percentage was 8.0%) and sealed, and reacted at 50 ° C for 3.8 h.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten was 96.15%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 53 After a molar ratio of CaO/WO 3 is 4.8, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed.
- the raw material is obtained, the calcium fluoride is added in an amount of 7% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 40 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 810 ° C for 1 h to obtain clinker and clinker.
- the clinker size is ⁇ 45 ⁇ m; the leaching equipment selects the leaching tank with stirring, and the saturated solution of ammonium carbonate is built in; the clinker is put into the leaching equipment, and ammonia water is added at the same time (the NH 3 in the leaching solution is made ) The mass percentage was 5.5%) and sealed, and reacted at 45 ° C for 6 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 98.63%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 54 After a molar ratio of CaO/WO 3 of 3.0, a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) was ground and mixed with clinker leaching residue. The raw material is obtained, and the calcium fluoride is added in an amount of 5% by mass of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 96 ⁇ m, and then calcined in a reducing atmosphere of the calciner at 880 ° C for 1 hour to obtain clinker and clinker.
- a scheelite WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%
- the clinker size is ⁇ 45 ⁇ m; the leaching equipment selects the leaching tank with stirring, and the saturated solution of ammonium carbonate is built in; the clinker is put into the leaching equipment, and ammonia water is added at the same time (the NH3 in the leaching solution is made) The mass percentage was 3.5%) and sealed, and reacted at 32 ° C for 3.8 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten is 96.75%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 55 After a molar ratio of CaO/WO 3 is 12, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed. The raw material is obtained, the calcium fluoride is added in an amount of 1.5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 36 ⁇ m, and then calcined in a neutral atmosphere of the roaster at 750 ° C for 5 hours to obtain clinker and clinker.
- the clinker size is ⁇ 100 ⁇ m; the leaching equipment selects the ball mill leacher, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.4 times; the clinker is put into the leaching equipment , reacted at 32 ° C for 3.8 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten is 86.35%.
- Example 56 Mixing a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) with limestone according to a (CaO+FeO)/WO 3 molecular ratio of 7. After the raw material is obtained, the raw material particle size is ⁇ 106 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 1000 ° C for 7 h to obtain clinker.
- the leaching equipment Select a ball mill leacher, built-in ammonium carbonate solution, ammonium carbonate concentration of 35g-(NH 4 ) 2 CO 3 /100g-H 2 O, and add ammonium bicarbonate according to the theoretical amount of 1.3 times; put the clinker into the leaching equipment, The reaction was carried out at 40 ° C for 9 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 95.99%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 57 After a molar ratio of CaO/WO 3 of 7, a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) was ground and mixed with clinker leaching residue. The raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 1200 ° C for 5 hours to obtain clinker. After the clinker is cooled to room temperature, it is ground by a vibration mill, and the clinker size is ⁇ 74 ⁇ m; the leaching equipment is selected.
- the ball mill leaching device was filled with a saturated solution of ammonium carbonate, and ammonium hydrogencarbonate was added at 1.4 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 20 ° C for 6 hours. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 78.01%.
- Example 58 According to the CaO/WO 3 molecular ratio of 8, a tungsten fine mud (WO 3 mass percentage of 16.22%) and the clinker leaching residue were ground and mixed to obtain a raw meal, and the raw material particle size was ⁇ 96 ⁇ m. Then, calcined in a reducing atmosphere of the calciner at 1400 ° C for 3 hours to obtain clinker, the clinker is cooled to room temperature, and then ground with a ball mill, the clinker size is ⁇ 45 ⁇ m; the leaching equipment selects a leaching tank with stirring, and a saturated solution of ammonium carbonate is built in.
- the clinker was placed in a leaching apparatus while adding ammonia water (so that the mass percentage of NH 3 in the leaching solution was 6%) and sealed, and reacted at 30 ° C for 4 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 81.51%. Then, similar to Example 3, but supplemented with ammonium carbonate, ammonium hydrogencarbonate, aqueous ammonia and CO 2 .
- Example 59 Grinding a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 3.5 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the roaster at 965 ° C for 8 hours to obtain clinker.
- the leaching equipment selects the ball mill leaching device, the built-in ammonium carbonate solution, the ammonium carbonate concentration is 20g-(NH 4 ) 2 CO 3 /100g-H 2 O, and the ammonium bicarbonate is added 1.4 times the theoretical amount; the clinker is placed
- the equipment was leached and reacted at 18 ° C for 6.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten is 92.96%. Then, similar to Example 3.
- Example 60 According to the (CaO+FeO)/WO 3 molecular ratio of 3.2, a black and white tungsten mixed ore (WO 3 mass percentage of 43.20%, Fe mass percentage of 7.18%) and clinker leaching residue and The calcium fluoride is ground and mixed to obtain a raw material.
- the calcium fluoride is added in an amount of 1.5% by mass of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then, in a roasting furnace neutral atmosphere at 850 ° C. After roasting for 3h, the clinker is obtained. After the clinker is cooled to room temperature, it is ground with a vibration mill. The clinker size is ⁇ 45 ⁇ m.
- the leaching equipment selects the ball mill leacher, the saturated solution of ammonium carbonate is built in, and the hydrogen carbonate is added according to the theoretical amount of 1.25 times.
- Ammonium; clinker was placed in a leaching apparatus and reacted at 28 ° C for 3.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten is 96.76%.
- the APT product meets the national 0 standard product standard.
- Example 61 grinding a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) with clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 9. After fine mixing, the raw material is obtained. The calcium fluoride is added in an amount of 1% by mass of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 950 ° C for 4 hours to obtain a cooked product.
- the clinker After the clinker is cooled to room temperature, it is ground with a ball mill, the clinker size is ⁇ 96 ⁇ m; the leaching equipment selects the ball mill leacher, and the saturated solution of ammonium carbonate is built in; the clinker is put into the leaching equipment, and the ammonia water is added at the same time (the NH in the leaching solution) The mass percentage of 3 was 5.9%) and sealed, and reacted at 47 ° C for 4.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 98.15%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 62 Grinding a scheelite (WO 3 mass percent of 49.53%, Fe mass percentage of 0.43%) with clinker leaching slag and calcium fluoride according to a CaO/WO 3 molecular ratio of 3.2 After fine mixing, the raw material is obtained. The calcium fluoride is added in an amount of 2.8% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 845 ° C for 5 hours to obtain a ripening.
- the clinker After the clinker is cooled to room temperature, it is ground with a ball mill, the clinker size is ⁇ 45 ⁇ m; the leaching equipment is selected with a stirring leaching tank, and the ammonium carbonate solution is built in, the ammonium carbonate concentration is 40g-(NH 4 ) 2 CO 3 /100g- H 2 O; The clinker was placed in a leaching apparatus while adding ammonia water (the mass percentage of NH 3 in the leaching solution was 4%) and sealed, and reacted at 45 ° C for 4.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten is 97.65%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 63 Grinding a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) with clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 3.8 After fine mixing, the raw material is obtained.
- the calcium fluoride is added in an amount of 1.2% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 120 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 870 ° C for 3 hours to obtain a cooked
- the clinker is cooled to room temperature, it is ground with a ball mill, the clinker size is ⁇ 45 ⁇ m;
- the leaching equipment selects the leaching tank with stirring, the built-in ammonium carbonate solution, and the ammonium carbonate concentration is 45g-(NH 4 ) 2 CO 3 /100g -H 2 O;
- the clinker was placed in a leaching apparatus while adding ammonia water (the mass percentage of NH 3 in the leaching solution was 7.9%) and sealed, and reacted at 5 ° C for 15 hours.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten is 93.15%. Then similar to Example 3 but supplemented with ammonium carbonate, ammonia and CO 2 .
- Example 64 According to the (CaO+FeO)/WO 3 molecular ratio of 4.5, a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue and fluorine
- the calcium is obtained by grinding and mixing to obtain a raw material.
- the calcium fluoride is added in an amount of 5.4% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a roasting furnace neutral atmosphere at 750 ° C.
- Example 65 According to the (CaO+FeO)/WO 3 molecular ratio of 3.4, a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue and fluorine After the calcium is finely mixed, the raw material is obtained, and the calcium fluoride is added in an amount of 3% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a roasting furnace neutral atmosphere at 760 ° C.
- Example 66 Grinding a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.2 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 980 ° C for 8 hours to obtain clinker, the clinker is cooled to room temperature, and then ground with a ball mill, the clinker size is ⁇ 45 ⁇ m; The leaching equipment was selected as a stirring leaching device, a saturated solution of ammonium carbonate was built in, and ammonium hydrogencarbonate was added at a theoretical amount of 4 times; the clinker was placed in a leaching apparatus and reacted at 50 ° C for 4 hours.
- the leaching slurry was suction filtered, and the filter cake was washed 4 times with pure water.
- the leaching rate of tungsten is 96.33%.
- the APT product meets the national 0 standard product standard.
- Example 67 Grinding limestone and fluorite with a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) at a molecular ratio of (CaO + FeO) / WO 3 of 4.1 After fine mixing, the raw material is obtained. The amount of fluorite added is 6% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 48 ⁇ m, and then calcined in a neutral atmosphere of the roaster at 970 ° C for 2 h to obtain clinker.
- a scheelite WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%
- the clinker size is ⁇ 40 ⁇ m; the leaching equipment is selected to stir the leaching device, and the ammonium carbonate solution is built in, the ammonium carbonate concentration is 25g-(NH 4 ) 2 CO 3 /100g-H 2 O, and ammonium bicarbonate was added at 1.4 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 80 ° C for 0.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed twice with pure water. The leaching rate of tungsten is 96.36%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 68 Grinding a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 6.5 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 53 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 990 ° C for 8 hours to obtain clinker.
- the clinker After the clinker is cooled to room temperature, it is ground by a rod mill, and the clinker size is ⁇ 74 ⁇ m; the leaching equipment was selected from a ball mill leacher, a saturated solution of ammonium carbonate was built in, and ammonium bicarbonate was added at a theoretical amount of 3 times; the clinker was placed in a leaching apparatus and reacted at 62 ° C for 4 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed 5 times with pure water. The leaching rate of tungsten was 97.70%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 69 According to the (CaO+FeO)/WO 3 molecular ratio of 4.7, a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue and firefly The stone is ground and mixed to obtain a raw material. The amount of fluorite added is 4% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 980 ° C for 2 h.
- the clinker After obtaining the clinker, the clinker is cooled to room temperature, ground with a ball mill, the clinker size is ⁇ 40 ⁇ m; the leaching equipment is selected to stir the leaching device, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.6 times; It was placed in a leaching apparatus and reacted at 75 ° C for 3.5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed twice with pure water. The leaching rate of tungsten was 97.01%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 70 Grinding a scheelite (WO 3 mass percent of 49.53%, Fe mass percentage of 0.43%) with a clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 3.2 After fine mixing, the raw material is obtained.
- the amount of calcium fluoride added is 2.5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 36 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 880 ° C for 1 h to obtain a cooked
- the clinker size is ⁇ 45 ⁇ m;
- the leaching equipment selects the leaching tank with stirring, and the saturated solution of ammonium carbonate is built in; the clinker is put into the leaching equipment, and the ammonia water is added at the same time (the leaching solution is made)
- the content of NH 3 was 6.7% by mass and sealed, and reacted at 90 ° C for 0.5 h.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten is 93.15%. Then similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 71 Grinding a scheelite (WO 3 mass percent of 49.53%, Fe mass percentage of 0.43%) with clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 3.8 After fine mixing, the raw material is obtained. The calcium fluoride is added in an amount of 3.6% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 90 ⁇ m, and then calcined in a roasting furnace neutral atmosphere at 860 ° C for 1 h to obtain a cooked product.
- a scheelite WO 3 mass percent of 49.53%, Fe mass percentage of 0.43%
- CaO/WO 3 molecular ratio of 3.8 After fine mixing, the raw material is obtained.
- the calcium fluoride is added in an amount of 3.6% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 90 ⁇ m, and then calcined in a roasting furnace neutral atmosphere at 860 ° C for 1 h
- the clinker size is ⁇ 45 ⁇ m; the leaching equipment is selected with a stirring leaching tank, a saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.1 times; clinker is added It was placed in a leaching apparatus and reacted at 45 ° C for 6 h. After the reaction was completed, the slurry was leached and filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 97.09%. Then, similar to Example 3, but supplemented with ammonium carbonate, ammonium hydrogencarbonate, aqueous ammonia and CO 2 .
- Example 72 Grinding a scheelite (WO 3 mass percent of 49.53%, Fe mass percentage of 0.43%) with clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 3.1 After fine mixing, the raw material is obtained. The calcium fluoride is added in an amount of 4.8% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a reducing atmosphere of the calciner at 880 ° C for 1 h to obtain a cooked product.
- the clinker After the clinker is cooled to room temperature, it is ground with a vibration mill, the clinker size is ⁇ 74 ⁇ m; the leaching equipment selects the ball mill leacher, and the saturated solution of ammonium carbonate is built in; the clinker is put into the leaching equipment, and the ammonia water is added at the same time (the leaching solution is made)
- the content of NH 3 was 7.5% by mass and was sealed, and reacted at 32 ° C for 3.8 h.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten is 97.75%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 73 Grinding a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) with clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 3.8 After fine mixing, the raw material is obtained.
- the amount of calcium fluoride added is 0.7% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 880 ° C for 9 hours to obtain a cooked
- the clinker is cooled to room temperature, it is ground with a ball mill, the clinker size is ⁇ 74 ⁇ m; the leaching equipment selects the ball mill leacher, and the saturated solution of ammonium carbonate is built in; the clinker is put into the leaching equipment, and the ammonia water is added at the same time (the NH in the leaching solution)
- the mass percentage of 3 was 8.6%) and sealed, and reacted at 32 ° C for 3.8 h.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten is 98.65%. Then similar to Example 3 but supplemented with ammonium carbonate, ammonia and CO 2 .
- Example 74 Grinding a scheelite (WO 3 mass percent content of 49.53%, Fe mass percentage of 0.43%) with clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 3.7 After fine mixing, the raw material is obtained. The calcium fluoride is added in an amount of 4.5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined at 800 ° C for 2.0 h in a baking furnace under an air atmosphere. , get clinker. After the clinker was cooled to room temperature, it was ground with a vibrating mill, and the clinker size was ⁇ 45 ⁇ m.
- Example 75 a black-and-white tungsten mixed ore (WO 3 mass percentage of 63.75%, Fe mass percentage of 5.90%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 4.5
- the calcium fluoride is finely mixed to obtain a raw material, and the calcium fluoride is added in an amount of 0.5% by mass of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then, in the shaft furnace, the weak reducing atmosphere Next, calcination at 1000 ° C for 3.0 h, clinker was obtained. After the clinker was cooled to room temperature, it was ground with a ball mill, and the clinker size was ⁇ 45 ⁇ m.
- Example 76 According to the (CaO+FeO)/WO 3 molecular ratio of 3.8, a certain black tungsten ore (WO 3 mass percentage of 60.40%, Fe mass percentage of 15.08%) and clinker leaching residue and fluorine After the calcium is ground and mixed, the raw material is obtained.
- the calcium fluoride is added in an amount of 3% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then, in the tubular baking furnace, neutral Under the atmosphere, calcination at 800 ° C for 6.0 h, clinker is obtained, the clinker is cooled to room temperature, and then ground with a rod mill, the clinker size is ⁇ 45 ⁇ m; the leaching equipment is selected with a stirring leaching tank, a saturated solution of ammonium carbonate is built, and Ammonium bicarbonate was added at 1.2 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 80 ° C for 4 h.
- Example 77 According to (CaO+FeO)/WO 3 molecular ratio of 3.5, a certain black tungsten ore (WO 3 mass percentage of 42.17%, Fe mass percentage of 11.34%) and clinker leaching residue and fluorine
- the calcium is subjected to finely mixing to obtain a raw material, and the amount of calcium fluoride added is 0.9% (mass percentage) of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 45 ⁇ m.
- Example 78 Grinding a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) with clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 6.0 After fine mixing, the raw material is obtained. The calcium fluoride is added in an amount of 2.4% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 30 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 870 ° C for 4 hours to obtain clinker.
- the clinker After the clinker is cooled to room temperature, it is ground with a planetary mill, the clinker size is ⁇ 74 ⁇ m; the leaching equipment selects the ball mill leacher, and the saturated solution of ammonium carbonate is built in; the clinker is put into the leaching equipment, and the ammonia water is added at the same time (the NH in the leaching solution) The mass percentage of 3 was 6.5%) and sealed, and reacted at 30 ° C for 4 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 98.09%. Then similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 79 Grinding a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to (CaO+FeO)/WO 3 molecular ratio of 7 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 25 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 1000 ° C for 7 hours to obtain clinker.
- the leaching equipment selects the ball mill leaching device, the built-in ammonium carbonate solution, the ammonium carbonate concentration is 60g-(NH 4 ) 2 CO 3 /100g-H 2 O, and the ammonium bicarbonate is added according to the theoretical amount of 1.3 times; the clinker is placed Into the leaching equipment, react at 40 ° C for 9 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 98.03%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 80 Grinding a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) with clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 3.0 After fine mixing, the raw material is obtained.
- the calcium fluoride is added in an amount of 3.2% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 950 ° C for 5 hours to obtain a ripe
- the clinker is cooled to room temperature, it is ground with a Raymond mill, the clinker size is ⁇ 8 ⁇ m; the leaching equipment is selected with a stirring leaching tank, and a saturated solution of ammonium carbonate is built in; the clinker is placed in the leaching equipment, and ammonia water is added at the same time ( The mass percentage of NH 3 in the leaching solution was 10.0%) and sealed, and the absolute pressure of the leaching system was controlled to be 1.0 atm, and the reaction was carried out at 20 ° C for 12 hours.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten is 96.20%. Then, similar to Example 3 but supplemented with ammonium bicarbonate, ammonia and CO 2 .
- Example 81 According to the CaO/WO 3 molecular ratio of 8, a tungsten fine mud (WO 3 mass percentage of 16.22%) and clinker leaching residue were ground and mixed to obtain a raw meal, and the raw material particle size was ⁇ 45 ⁇ m. Then, calcined in a reducing atmosphere of the calciner at 950 ° C for 3 h to obtain clinker, the clinker is cooled to room temperature, and then ground with a ball mill, the clinker size is ⁇ 45 ⁇ m; the leaching equipment selects a leaching tank with stirring, and a saturated solution of ammonium carbonate is built in.
- the clinker was placed in a leaching apparatus while adding ammonia water (the mass percentage of NH 3 in the leaching solution was 6.3%) and sealed, and reacted at 35 ° C for 15 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 91.51%. Then, add ammonia and CO 2 .
- Example 82 According to the (CaO+FeO)/WO 3 molecular ratio of 3.6, a scheelite (WO 3 mass percentage of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue and fluorine
- the calcium is subjected to finely mixing to obtain a raw material, and the calcium fluoride is added in an amount of 4.1% by mass of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 965 ° C.
- Example 83 According to the (CaO+FeO)/WO 3 molecular ratio of 3.3, a black and white tungsten mixed ore (WO 3 mass percentage of 43.20%, Fe mass percentage of 7.18%), and clinker leaching residue
- the calcium fluoride is finely mixed to obtain a raw material, and the calcium fluoride is added in an amount of 2.2% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then in a roasting furnace neutral atmosphere at 850 ° C After calcination for 3h, the clinker is obtained. After the clinker is cooled to room temperature, it is ground with a rod mill. The clinker size is ⁇ 45 ⁇ m.
- the leaching equipment selects the ball mill leacher, and the ammonium carbonate solution is built in.
- the ammonium carbonate concentration is 40g-(NH 4 ) 2 . CO 3 /100g-H 2 O, and ammonium bicarbonate was added at 1.25 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 42 ° C for 20 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 98.76%. Then, similar to Example 3 but supplemented with ammonium carbonate and ammonium bicarbonate, the APT product meets the national 0 grade standard requirements.
- Example 84 grinding a scheelite (WO 3 mass percentage of 49.53%, Fe mass percentage of 0.43%) with clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 9. After fine mixing, the raw material is obtained.
- the amount of calcium fluoride added is 0.55% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 30 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 950 ° C for 4 hours to obtain a cooked
- the clinker is cooled to room temperature, it is ground with a ball mill, the clinker size is ⁇ 45 ⁇ m;
- the leaching equipment selects the leaching tank with stirring, and the mixed solution of saturated ammonium carbonate and ammonium tungstate containing 60g/L WO 3 is built; The leaching equipment was placed, and ammonia water was added (the mass percentage of NH 3 in the leaching solution was 9.1%) and sealed, and reacted at 37 ° C for 4.5 hours.
- Example 3 After the reaction was completed, the slurry was leached and filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 98.72%. Then similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 85 After a molar ratio of CaO/WO 3 is 2.7, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed.
- the raw material is obtained, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the baking furnace at 845 ° C for 2.5 h to obtain clinker, and the clinker is cooled to room temperature, and then ground by a hanging roll pulverizer, and the clinker particle size is ⁇ 74 ⁇ m;
- the leaching equipment was selected with a stirring leaching tank, a saturated solution of ammonium carbonate was built in, and ammonium bicarbonate was added at 1.2 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 45 ° C for 4.5 h.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten is 81.65%. Then similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 86 Grinding a scheelite (WO 3 mass percent of 49.53%, Fe mass percentage of 0.43%) with a clinker leaching residue and calcium fluoride according to a CaO/WO 3 molecular ratio of 3.8 After fine mixing, the raw material is obtained.
- the calcium fluoride is added in an amount of 1.5% by mass of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 870 ° C for 1 h to obtain a cooked After the clinker is cooled to room temperature, it is ground with a ball mill, the clinker size is ⁇ 45 ⁇ m; the leaching equipment selects the leaching tank with ball mill, and the supersaturated ammonium carbonate slurry is built in.
- the concentration of ammonium carbonate is 100g (NH 4 ) 2 CO 3 /100g H 2 O;
- the clinker was placed in a leaching apparatus while adding ammonia water (so that the mass percentage of NH 3 in the leaching solution was 6.5%) and sealed, and reacted at 52 ° C for 3.8 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten is 98.25%. Then similar to Example 3 but supplemented with ammonium carbonate, ammonium hydrogencarbonate, aqueous ammonia and CO 2 .
- Example 87 Grinding limestone and fluorite with a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) at a molecular ratio of (CaO + FeO) / WO 3 of 4.5 After fine mixing, the raw material is obtained. The amount of fluorite added is 2.6% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a reducing atmosphere of the calciner at 920 ° C for 2 h to obtain clinker.
- the clinker size is ⁇ 8 ⁇ m; the leaching equipment is selected to stir the leaching device, the saturated solution of ammonium carbonate is built in, and ammonium bicarbonate is added according to the theoretical amount of 1.2 times; It was placed in a leaching apparatus and reacted at 38 ° C for 5 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed twice with pure water. The leaching rate of tungsten was 98.12%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 88 a scheelite (WO 3 mass percent of 52.33%, Fe mass percentage of 2.04%) and clinker of Example 86 at a molecular ratio of (CaO + FeO) / WO 3 of 3.4
- the slag after leaching (mainly CaCO 3 ) and calcium fluoride are ground and mixed to obtain a raw meal.
- the amount of calcium fluoride added is 4.1% (mass percentage) of the dry tungsten mineral raw material, and the raw material particle size is ⁇ 100 ⁇ m. Then, it is calcined in a neutral atmosphere of the calciner at 960 ° C for 2 h to obtain clinker.
- the leaching equipment is selected to be a stirred leaching device, and a saturated solution of ammonium carbonate is built in. And adding ammonium bicarbonate at 1.2 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 50 ° C for 3 h. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed 5 times with pure water. The leaching rate of tungsten was 98.39%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 89 a scheelite (WO 3 mass percent of 52.33%, Fe mass percent of 2.04%) and a clinker of Example 88 at a molecular ratio of (CaO + FeO) / WO 3 of 4.2
- the slag and the calcium fluoride after leaching are ground and mixed to obtain a raw material, and the calcium fluoride is added in an amount of 0.2% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 74 ⁇ m, and then, in the baking furnace The atmosphere is calcined at 980 ° C for 1.5 h to obtain clinker.
- the clinker After the clinker is cooled to room temperature, it is ground by a vibrating mill with a clinker size of ⁇ 85 ⁇ m.
- the leaching equipment selects a ball mill leacher with a supersaturated ammonium carbonate slurry and the ammonium carbonate concentration is 120 g of (NH 4 ) 2 CO 3 /100 g of H 2 O, and ammonium bicarbonate was added at 1.5 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 70 ° C for 6 h. After the reaction was completed, the slurry was leached and filtered, and the filter cake was washed 4 times with pure water. The leaching rate of tungsten is 97.23%. Then, similar to Example 3 but supplemented with ammonium carbonate and ammonium bicarbonate, the APT product meets the national 0 grade standard requirements.
- Example 90 Grinding a scheelite (WO 3 mass percent content of 52.33%, Fe mass percentage of 2.04%) and clinker leaching residue according to a (CaO+FeO)/WO 3 molecular ratio of 7 After fine mixing, the raw material is obtained, the raw material particle size is ⁇ 80 ⁇ m, and then calcined in a neutral atmosphere of the calciner at 1000 ° C for 7 hours to obtain clinker. After the clinker is cooled to room temperature, it is ground by a vibration mill, and the clinker size is ⁇ 45 ⁇ m.
- the leaching equipment was selected from a ball mill leaching device, a saturated solution of ammonium carbonate was built in, and ammonium hydrogencarbonate was added at 1.3 times the theoretical amount; the clinker was placed in a leaching apparatus and reacted at 40 ° C for 24 hours. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten is 98.66%. Then, similar to the embodiment 3, the APT product meets the national 0 standard product standard.
- Example 91 After a molar ratio of CaO/WO 3 is 4, a scheelite (WO 3 mass percent content is 49.53%, Fe mass percentage is 0.43%) and the clinker leaching residue is ground and mixed. The raw material is obtained, the raw material particle size is ⁇ 53 ⁇ m, and then calcined in a neutral atmosphere of the roaster at 950 ° C for 10 h to obtain clinker.
- the leaching equipment selection belt The stirred leaching tank was filled with a saturated solution of ammonium carbonate; the clinker was placed in a leaching apparatus, and ammonia water was added (the mass percentage of NH 3 in the leaching solution was 13.0%) and sealed, and reacted at 40 ° C for 20 hours. After the reaction was completed, the leaching slurry was suction filtered, and the filter cake was washed three times with pure water. The leaching rate of tungsten was 99.01%. Then, similar to Example 3 but supplemented with ammonia and CO 2 .
- Example 92 according to the CaO/WO 3 molecular ratio of 8, a tungsten fine mud (WO 3 mass percentage of 16.22%) and the clinker leaching residue and calcium fluoride were finely mixed to obtain a raw material, fluorine
- the amount of calcium added is 6.5% (mass percentage) of the dry tungsten mineral raw material, the raw material particle size is ⁇ 45 ⁇ m, and then calcined in a reducing atmosphere of the baking furnace at 750 ° C for 0.5 h to obtain clinker, and after the clinker is cooled to room temperature, Grinding with a centrifugal mill, clinker size ⁇ 45 ⁇ m; leaching equipment selected ball mill leacher, built-in saturated ammonium carbonate solution; clinker into the leaching equipment, while adding ammonia (the mass percentage of NH 3 in the leaching solution is 8.5%) and sealed, reacted at 45 ° C for 4 h.
- the leaching slurry was suction filtered, and the filter cake was washed three times with pure water.
- the leaching rate of tungsten was 94.51%. Then, similar to Example 3, but supplemented with ammonium carbonate, ammonium hydrogencarbonate, aqueous ammonia and CO 2 .
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Abstract
一种钨矿物原料(100)的冶金工艺,采用有助于形成局部工艺循环的弱碱浸出剂,其浸出液在蒸发结晶过程中产生两种或两种以上的气体,各气体又可以重新参与合成该浸出剂,结晶后的分离洗涤液同样作为浸出剂循环使用;以及采用一转型配料,其通过与钨矿物原料(100)发生化学反应,可使得钨元素改含在容易被所述浸出剂溶解的中间物质中,而浸出渣中也含有配料元素,以便于至少部分浸出渣可以作为配料循环使用,为此,该工艺包含多个闭路循环,全程无废水排放。
Description
本发明涉及一种由钨矿物原料制备APT的方法,属于钨冶炼技术领域。
术语“生料”是指钨矿物原料、配料,按比例配合后,并磨至一定细度的混合物料。
术语“熟料”是指钨矿物原料、配料经磨细、混合成生料,再经高温焙烧后所得的物料。
术语“矿化剂”是指在生料焙烧过程中能加速钨矿物原料与配料之间的反应或降低焙烧温度的物质。
现有技术中,制备APT的工业方法主要包括如下步骤:通过苛性钠或苏打分解钨矿物原料,获得粗钨酸钠溶液;通过溶液净化-离子交换或溶剂萃取转型(或者通过离子交换或溶剂萃取除杂并转型),获得纯钨酸铵溶液;再通过蒸发结晶,获得APT产品。
现有技术都存在如下本质缺陷:均采用不循环或半循环工艺体系,没有实现全部循环工艺。现有技术至少存在以下技术问题:必需设置废水排出口,废水污染问题无法彻底根除;辅助物料大都为一次性消耗品,且浸出过程的浸出剂过量使用,这些辅助物料在相应工艺步骤反应完毕后要么直接外排、要么需要使用对应的酸或者碱中和后再外排,辅助物料消耗多,生产成本高;在废水中不可避免地带出部分钨元素,钨元素回收率低;设备投资大,工艺流程长,生产率较低,较难实现连续生产。
在这样的APT制备过程中,辅助原料消耗较大,且产生大量废水;钨酸钠溶液转型过程中产生大量的高盐废液,蒸发结晶母液产生氨氮废水。
如果把有废水排放的开路流程变成没有废水排放的闭路流程,不是没有技术上的可能性,而是投入的资金甚至可能大于利润,为此,现有技术中,企业不得不选择排放,结果导致严重的环境污染。
发明内容
本发明的目的是提供一种从钨矿物原料制备APT的方法,其流程短、溶液可循环利用、环境污染几乎被根除、成本低、易于产业化。
为此,根据本发明的一个方面,提供了一种从钨矿物原料制备APT的方法,该方法包括如下步骤:
1)将钨矿物原料、配料磨细后,混合均匀制备生料;
2)对生料进行焙烧,获得熟料,并将熟料进行破碎,磨细;
3)以碳酸铵、碳酸铵-碳酸氢铵、碳酸铵-钨酸铵、碳酸铵-CO2、碳酸铵-氨水-CO2、碳酸铵-氨水、碳酸铵-碳酸氢铵-钨酸铵、碳酸铵-碳酸氢铵-钨酸铵-CO2、碳酸铵-氨水-钨酸铵、碳酸铵-钨酸铵-CO2、和/或碳酸铵-氨水-钨酸铵-CO2体系浸出熟料;
4)浸出浆液经固液分离及渣相洗涤,得到粗钨酸铵溶液和浸出渣,部分浸出渣作为配料返回步骤1)进行生料配置,剩余部分堆存;
5)粗钨酸铵溶液净化除杂;
6)净化后溶液采用蒸发结晶析出APT,同时获得氨气和二氧化碳气体;
7)对结晶后的浆液进行液固分离和/或洗涤后,得到结晶母液和固相,固相经水和/或铵盐溶液洗涤,烘干后即获得APT产品(或进入下一级溶解、结晶、提纯子系统),结晶母液与收集的步骤6)得到的氨气和二氧化碳一起返回到熟料的浸出步骤3),并在补充消耗的碳酸铵(可由碳酸氢铵或氨水和CO2部分替代)后循环浸出熟料。
优选地,所述的钨矿物原料包括,白钨矿、黑钨矿、黑白钨混合矿、和/或钨细泥;优选地,生料配制时,浸出渣的加入量按生料中CaO/WO3或(CaO+FeO)/WO3或(CaO+MnO)/WO3或(CaO+FeO+MnO)/WO3分子比至少为1.0计,优选为1.5-6.0,更优选为3.0-4.0,更优选为3.3-3.6;生料粒度不受特别限制,优选为不大于200μm,更优选为不大于100μm,更优选为不大于40μm;生料焙烧时,温度为不低于500℃,优选为800-1050℃,更优选为850-950℃;
优选地,在生料配制过程中添加矿化剂,优选为氟化钙,以加速钨矿物原料与配料之间的反应,显著降低焙烧温度;
优选地,生料焙烧的时间为0.5-8.0h,优选为1.0-3.0h,更优选为2.0h;钨矿物原料为白钨矿时,焙烧气氛不受特别限制,优选为中性或氧化性气氛;
优选地,钨矿物原料为黑钨矿、黑白钨混合矿、和/或钨细泥时,焙烧气氛为中性或还原性气氛,优选为中性气氛;熟料的粒度不受特别限制,优选为不大于200μm,再优选为不大于74μm,再优选为不大于45μm;
优选地,浸出体系中的CO2一部分来自生料焙烧过程所产生的炉(窑)气或者是商品CO2,另一部分来自钨酸铵溶液蒸发结晶过程所产生的CO2;
优选地,CO2可在浸出过程中通入,也可以在浸出前通入。
优选地,浸出初始体系中碳酸铵浓度大于20g-(NH4)2CO3/100g-H2O,优选为该体系下其饱和溶液的浓度,而碳酸氢铵则以溶液或固体的形式加入,碳酸氢铵的加入量不受特别限制,优选为不少于使熟料中的钙转化为CaCO3所需量(理论量)的1.0倍,更优选为理论量的1.1-1.4倍,钨酸铵浓度无特别限制,只要能确保熟料中钨充分浸出后所得溶液中的钨酸铵浓度不超过该体系下的平衡浓度即可,氨水的加入量也不受特别限制,优选的浸出初始体系中NH3的质量百分含量为0-28%,更优选为5-20%,更优选为5-10%;熟料的浸出过程在密闭体系中进行,以碳酸铵体系、碳酸铵-碳酸氢铵体系、碳酸铵-氨水体系、碳酸铵-碳酸氢铵-钨酸铵体系、碳酸铵-氨水-钨酸铵体系和碳酸铵-钨酸铵体系浸出熟料时,反应体系的绝对压力不受特别限制,以碳酸铵-CO2体系、碳酸铵-碳酸氢铵-CO2体系、碳酸铵-氨水-CO2体系、碳酸铵-钨酸铵-CO2体系、碳酸铵-氨水-钨酸铵-CO2体系和碳酸铵-碳酸氢铵-钨酸铵-CO2体系浸出熟料时,需控制反应体系的绝对压力不小于1atm,优选为2atm;
优选地,浸出温度不低于5℃,优选为10-80℃,更优选为20-70℃,更优选为30-50℃;
优选地,浸出时间不受特别限制,只要能确保熟料中钨能充分浸出即可,优选地浸出时间为0.5-8.0h,更优选地浸出时间为2-5h;净化除杂过程包括除钼、磷、锡、砷、硅、铁、钠、钾、铋、锑、钙、镁过程的至少一种;
根据本发明的另外一个方面,提供了一种采用权利要求1所述的方法制备APT的系统,包括:
1)磨矿设备A,钨矿物原料、配料经配料计量后,采用磨矿设备A将各种原料磨细、混匀,制备具有一定细度和均匀度的生料;
2)焙烧窑(炉),将制备的生料加入焙烧窑(炉)中焙烧,冷却后得到熟料;
3)磨矿设备B,烧成的熟料采用磨矿设备B磨细;
4)浸出设备,熟料在浸出设备中进行浸出;
5)过滤设备,浸出浆液采用过滤设备进行过滤洗涤;
6)除杂设备,粗钨酸铵溶液在除杂设备内净化除杂;以及
7)结晶设备,钨酸铵精制液在结晶设备内蒸发结晶。
优选地,所述磨矿设备A选自:振动磨机、球磨机、棒磨机、自磨机、搅拌磨机、悬辊粉碎机、塔式磨机、胶体磨机、离心磨机、高压盘磨机、雷蒙磨机、气流粉碎机。
优选地,所述焙烧窑(炉)包括:静态焙烧窑(炉)和动态焙烧窑(炉)。
优选地,所述磨矿设备B选自:对辊机、振动磨机、球磨机、棒磨机、自磨机、搅拌磨机、悬辊粉碎机、塔式磨机、胶体磨机、离心磨机、高压盘磨机、雷蒙磨机、气流粉碎机。
优选地,所述浸出设备可以是单独一个浸出设备,也可以2-4个浸出设备串联使用。
优选地,所述浸出设备可以是搅拌浸出设备,也可以是球磨浸出设备。
优选地,所述浸出设备可以密封,并能够承受4atm压力。
优选地,所述过滤设备是抽滤设备、压滤设备、自然过滤槽。
优选地,所述除杂设备是除杂罐、过滤设备、沉降槽。
优选地,所述除杂罐内设有搅拌装置。
本发明相对于现行APT的工业生产方法,其优点在于:
1)实现了由钨矿物原料制备APT过程中溶液的闭路循环,从而理论上可根除APT生产过程中由于大量废水排放而造成的环境污染问题;
2)通过将钨矿物原料焙烧转型,使钨元素改含在容易被碳酸铵盐溶液浸出的物质中,实现了钨的低温浸出,降低浸出过程中的能量消耗和成本,同时,浸出渣又可以作为钨矿物原料转型过程中的配料而循环使用;
3)采用低成本、易循环的碳酸铵盐体系浸出钨矿物熟料,直接得到钨酸铵溶液,取消了从
钨酸钠溶液到钨酸铵溶液的转型步骤,流程简单;
4)由于多种辅助物料的循环利用,辅助物料消耗量大幅度减少,加工费用大幅度降低;
5)操作简单,便于控制,易于工业应用。
根据本发明,用“碳酸铵-碳酸氢铵-钨酸铵”或“碳酸铵-钨酸铵-CO2”或“碳酸铵-氨水-钨酸铵”或“碳酸铵-氨水”或“碳酸铵”或“碳酸铵-碳酸氢铵”或“碳酸铵-氨水-CO2”或“碳酸铵-氨水-钨酸铵-CO2”或“碳酸铵-碳酸氢铵-钨酸铵-CO2”或“碳酸铵-CO2”或“碳酸铵-钨酸铵”或“碳酸铵-碳酸氢铵-CO2”体系作为浸出液非显而易见,这是因为:弱碱性体系处理不了白钨矿、黑钨矿、黑白钨混合矿和钨细泥等化学反应活性较低的原料(或处理效率极低)。钨冶炼工业目前一般采用强酸(如盐酸)或强碱(如氢氧化钠)性体系、并且在高温、高压环境下浸出钨矿物原料,而“碳酸铵-碳酸氢铵-钨酸铵”、“碳酸铵-钨酸铵-CO2”、“碳酸铵-氨水-钨酸铵”、“碳酸铵-氨水”、“碳酸铵”、“碳酸铵-碳酸氢铵”、“碳酸铵-氨水-CO2”、“碳酸铵-氨水-钨酸铵-CO2”、“碳酸铵-碳酸氢铵-钨酸铵-CO2”、“碳酸铵-CO2”、“碳酸铵-钨酸铵”和“碳酸铵-碳酸氢铵-CO2”体系均属于弱碱性体系,必须经过原料转型步骤才能实现浸出。
根据本发明,选用“碳酸铵-碳酸氢铵-钨酸铵”或“碳酸铵-钨酸铵-CO2”或“碳酸铵-氨水-钨酸铵”或“碳酸铵-氨水”或“碳酸铵”或“碳酸铵-碳酸氢铵”或“碳酸铵-氨水-CO2”或“碳酸铵-氨水-钨酸铵-CO2”或“碳酸铵-碳酸氢铵-钨酸铵-CO2”或“碳酸铵-CO2”或“碳酸铵-钨酸铵”或“碳酸铵-碳酸氢铵-CO2”体系进行浸出,浸出体系物料在结晶步骤后转化成氨气和二氧化碳,恰好能补充入浸出体系,从而实现了辅助物料的全部循环利用,彻底摈弃了传统的开路不循环体系或开路半循环体系,根除了污染排放,真正实现了绿色冶金。
根据本发明,不仅在浸出液固比较高时可获得好的钨浸出效果,在浸出液固比小于10时,熟料中钨的浸出率也不下降,所得浸出液中WO3的浓度仍然足够工业化生产。
根据本发明,采用“碳酸铵-碳酸氢铵-钨酸铵”或“碳酸铵-钨酸铵-CO2”或“碳酸铵-氨水-钨酸铵”或“碳酸铵-氨水”或“碳酸铵”或“碳酸铵-碳酸氢铵”或“碳酸铵-氨水-CO2”或“碳酸铵-氨水-钨酸铵-CO2”或“碳酸铵-碳酸氢铵-钨酸铵-CO2”或“碳酸铵-CO2”或“碳酸铵-钨酸铵”或“碳酸铵-碳酸氢铵-CO2”体系浸出熟料,在浸出液固比为4时,仍能获得较好的钨浸出效果,所得浸出液中WO3浓度较高,非常适应于工业化生产。
根据本发明,采用闭路循环工艺,只设置废渣排出口,不再需设置废水排出口,废水排放的污染问题得到了彻底根除。
根据本发明,辅助物料不再是一次性消耗品,浸出过程的浸出剂循环使用,即使辅助物料过量使用,在相应工艺步骤反应完毕后也不再直接外排,不再需要使用对应的酸或者碱中和,因此,辅助物料消耗大幅减少,生产成本大幅降低。
根据本发明,实现了循环冶金工艺,传统工艺体系的“废水”被吸干榨净,彻底避免部分钨元素被白白排放掉,因此,钨元素回收率也提高了。
根据本发明,可实现集成化生产,车间的工作环境可大幅改善,设备投资回报率明显提高,工艺流程变短,生产率得到大幅提高,可以实现连续的自动化生产。
根据本发明,增加了钨矿物原料的预处理工序,采用“碳酸铵-碳酸氢铵-钨酸铵”或“碳酸铵-钨酸铵-CO2”或“碳酸铵-氨水-钨酸铵”或“碳酸铵-氨水”或“碳酸铵”或“碳酸铵-碳酸氢铵”或“碳酸铵-氨水-CO2”或“碳酸铵-氨水-钨酸铵-CO2”或“碳酸铵-碳酸氢铵-钨酸铵-CO2”或“碳酸铵-CO2”或“碳酸铵-钨酸铵”或“碳酸铵-碳酸氢铵-CO2”体系浸出钨矿物熟料,浸出条件温和,浸出剂便宜、易得,辅助物料可循环利用,在理论上可消除生产过程中的废水排放。
根据本发明,完全脱离了现有技术,提出了一种全新的制备APT的理念和工艺,省去会产生大量废水的钨酸钠溶液转型步骤,直接得到钨酸铵溶液,从根本上消除了APT生产过程中废水的排放,并实现了辅助物料和溶液的循环利用。
根据本发明,工艺流程简单,操作方便,生产成本低,无废水排放,环境污染降低至最低程度。
图1为根据本发明的一种由钨矿物原料制备APT的系统的结构原理示意图。
图2为根据本发明的一种由钨矿物原料制备APT的工艺流程图。
下面结合附图1-2对本发明的实施例作进一步说明。
如图1所示,本发明的含钨矿物原料的冶金工艺包括以下步骤:
使含W矿物原料100与配料MN(M表示正离子,N表示负离子)配比成生料101;
焙烧生料200,促其发生化学反应,以转型为含M和含W离子的熟料,从而使熟料获得高的化学反应活性;
采用弱碱AN(A为正离子)溶液浸出(彻底摒弃传统的过量强碱浸出偏见)熟料,以使熟料浸出300,并且在循环反应中,回收各环节反馈回来的溶液,以及按照实际需要补充消耗的弱碱AN;
对浸出浆液进行固液分离400,得到含A和含W离子的粗溶液和含M的浸出渣,对渣相洗涤,洗涤液反馈至熟料浸出环节(第I闭环),根据实际需要,取至少部分浸出渣反馈至生料配置环节(第II闭环)作为配料,如果浸出渣有剩余部分,则堆存;
对含A和含W离子的粗溶液进行至少一级净化除杂500(优选地,最后一级可加设抽风装置);
对净化后的溶液进行蒸发结晶600,以析出含W元素的中间产品;同时,将释放出与A元素相关的气体和与N元素相关的气体返回至浸出熟料300的步骤(第III闭环),而蒸发出的水反馈至浸出浆液300的固液分离环节(第IV闭环);
对结晶后的浆液进行液固分离700,以得到结晶母液和固相,固相经水和/或铵盐溶液洗涤,烘干后即获得含W元素的最终产品(优选地对固相进行再次溶解和结晶,以得到纯度更高的最终产品);而结晶母液也返回至浸出熟料的步骤(第V闭环),
为此,该工艺包含多个闭路循环,全程无废水排放。
如图2所示,本发明的钨矿物原料的冶金系统依次包括:
生料制备装置10,其具有矿物原料入口11和配料入口12(优选还设有矿化剂入口13;优选地,各入口还设有计量器)、生料磨细装置(含混匀器)14、生料出口15、和浸出渣接收口16;
焙烧窑(炉)20,其经喂料计量器和生料仓与生料出口15连通,具有加热装置、保温装置(优选还包括冷却装置21)、气氛(氧化性气氛、还原性气氛、中性气氛)控制装置和粗熟料出口22;
熟料磨细装置30,其经熟料仓与粗熟料出口22连通,具有磨矿器和细熟料出口31;
浸出装置40,其与细熟料出口连通31,具有浸出剂入口41、浸出浆液出口42、反馈气体回收口43、结晶浆液分离洗涤液回收口44、渣相洗涤液回收口45、晶种入口46(优选地,还包括二氧化碳通入口47);
浸出浆液的固液分离装置(优选过滤装置),其与浸出浆液出口42连通,具有含配料元素的浸出渣的过滤洗涤器50、含钨元素的粗溶液出口51、浸出渣反馈口52、至剩余浸出渣堆存库的出口53、洗液反馈出口54、蒸发结晶冷凝水的接收口55,该固液分离装置在反馈至生料制备装置10的浸出渣接收口16的途中与浸出装置40的晶种入口46连通;
至少一级净化除杂装置60,第一级的入口61与含钨元素的粗溶液出口51连通,各级具有净化除杂剂入口以及杂质收集器,最后一级具有含钨元素的精溶液出口62(优选地,最后一级加设抽风装置);
结晶装置70,其入口71与含钨元素的粗溶液出口62连通,具有结晶浆液出口72、反馈至浸出装置的气体反馈口73、和冷凝水出口74(优选具有钨产品的粗溶液蒸发结晶控制器);
结晶浆液的液固分离装置80,其与结晶浆液出口72连通,具有结晶母液返回至浸出装置40的出口81、固相洗水入口82、和钨产品的出口83(优选地,与下一级溶解、结晶、提纯子系统连通)。
根据本发明,将钨矿物原料与一定量的含钙物质和矿化剂经磨细后,混合均匀获得生料;生料配制时,含钙物质的加入量按生料中CaO/WO3或(CaO+FeO)/WO3或(CaO+MnO)/WO3或(CaO+FeO+MnO)/WO3分子比至少为1.0计,优选为1.5-6.0,更优选为3.0-4.0,更优选为3.3-3.6;
生料配制时,配入的矿化剂为氟化物,优选地为氟化钙,氟化钙的加入量为干钨矿物原料量的0.5-7%(质量百分数),优选1-3%(质量百分数);生料粒度不受特别限制,优选为不大于200μm,更优选为不大于100μm,更优选为不大于40μm;生料焙烧温度不低于500℃,优选地生料焙烧温度为800~1050℃,更优选为850~950℃;焙烧时间不受特别限制,温度低则需延长焙烧时间,为使生料中的钨充分转化为Ca3WO6和/或Ca2FeWO6和/或Ca2MnWO6,优选地焙烧时间为0.5-8.0h,更优选为1.0~3.0h,更优选地在850~950℃下焙烧2.0h。
对于白钨矿原料,焙烧气氛不受特别限制,优选为中性或氧化性气氛;对于黑钨矿、黑白
钨混合矿和/或钨细泥原料,焙烧气氛为中性或还原性气氛,优选为中性气氛。本发明将含Ca3WO6和/或Ca2FeWO6和/或Ca2MnWO6的混合物料加入到铵盐溶液体系中,在密闭条件下浸出,浸出完成后,浸出浆液经分离洗涤,得到钨酸铵溶液。
优选地,所述Ca3WO6和/或Ca2FeWO6和/或Ca2MnWO6可为人工合成的纯化合物,也可以是钨矿物原料经处理后得到的含Ca3WO6和/或Ca2FeWO6和/或Ca2MnWO6的混合物(熟料);Ca3WO6和/或Ca2FeWO6和/或Ca2MnWO6的混合物料的粒度不大于200μm,优选为小于45μm;所述的铵盐溶液体系,可以是碳酸铵-碳酸氢铵-钨酸铵体系、碳酸铵-钨酸铵-CO2体系、碳酸铵-氨水-钨酸铵体系、碳酸铵-氨水体系、碳酸铵体系、碳酸铵-碳酸氢铵体系、碳酸铵-氨水-CO2体系、碳酸铵-氨水-钨酸铵-CO2体系、碳酸铵-碳酸氢铵-钨酸铵-CO2体系、碳酸铵-CO2体系、碳酸铵-钨酸铵体系、也可以是碳酸铵-碳酸氢铵-CO2体系。
优选地,用碳酸铵体系、碳酸铵-碳酸氢铵体系、碳酸铵-氨水体系、碳酸铵-碳酸氢铵-钨酸铵体系、碳酸铵-氨水-钨酸铵体系和碳酸铵-钨酸铵体系浸出Ca3WO6和/或Ca2FeWO6和/或Ca2MnWO6时,浸出体系的绝对压力不受特别限制;用碳酸铵-CO2体系、碳酸铵-碳酸氢铵-CO2体系、碳酸铵-氨水-CO2体系、碳酸铵-钨酸铵-CO2体系、碳酸铵-氨水-钨酸铵-CO2体系和碳酸铵-碳酸氢铵-钨酸铵-CO2体系浸出Ca3WO6和/或Ca2FeWO6和/或Ca2MnWO6时,在浸出过程中通入CO2,控制浸出体系的绝对压力不小于1atm,优选为1.5-2.5atm,更优选为2atm。优选地,浸出体系碳酸铵浓度大于20g-(NH4)2CO3/100g-H2O,优选为饱和的碳酸铵溶液。
优选地,所述碳酸铵-钨酸铵-碳酸氢铵、碳酸铵-钨酸铵-CO2、碳酸铵-氨水-钨酸铵、碳酸铵-钨酸铵、碳酸铵-氨水-钨酸铵-CO2和碳酸铵-碳酸氢铵-钨酸铵-CO2溶液体系中,钨酸铵浓度也不受特别限制,只要满足Ca3WO6和/或Ca2FeWO6和/或Ca2MnWO6中的钨充分浸出后,所得溶液中钨酸铵浓度不超过其在该体系中的溶解度。
优选地,所述碳酸铵-碳酸氢铵、碳酸铵-钨酸铵-碳酸氢铵、碳酸铵-碳酸氢铵-CO2和碳酸铵-碳酸氢铵-钨酸铵-CO2溶液体系,碳酸氢铵加入量不受特别限制,优选为不少于理论量的1.0倍,更优选为理论量的1.1~1.4倍。
优选地,所述碳酸铵-氨水-钨酸铵、碳酸铵-氨水-钨酸铵-CO2、碳酸铵-氨水和碳酸铵-氨水-CO2溶液体系中,氨水的加入量也不受特别限制,优选的浸出初始体系中NH3的质量百分含量为0-28%,更优选为5-20%,更优选为5-10%。
优选地,控制浸出体系pH不小于8.0。浸出温度不低于5℃,优选为10-80℃,更优选为20-70℃,更优选为30-50℃;浸出时间不受特别限制,只要能使Ca3WO6和/或Ca2FeWO6和/或Ca2MnWO6中的钨充分浸出即可,优选为0.5-8.0h,更优选地浸出时间为2.0-5.0h。
优选地,浸出体系初始液固比不低于1:1mL/g,优选为10:1-4:1mL/g。
优选地,可以通过多段加料的方式,降低浸出体系的最终液固比,优选地通过两段加料,控制最终浸出体系的液固比为3:1~4:1mL/g。优选地,所述的碳酸铵溶液也可由碳酸氢铵溶液和氨水、或氨水和CO2部分替代。
当溶液中的(NH4)2WO4浓度较高时,尤其是有大量NH4OH存在的情况下,(NH4)2WO4会与浸出过程生成的高活性CaCO3发生二次反应,生成难以被碳酸铵盐溶液浸出的CaWO4,导致钨损失。主要反应可能是:
Ca(OH)2+(NH4)2WO4=CaWO4+2NH4OH (2)
反应(2)较易进行,而一般情况下反应(1)难以进行,但在Ca3WO6的浸出过程中新生的CaCO3活性高,反应(1)则有可能进行,且随着浸出过程的进行NH4OH和(NH4)2WO4的浓度不断增加,反应(1)和反应(2)得以强化,最终导致(NH4)2WO4浓度较高时钨的损失增加。因此,在密闭的浸出体系中通入CO2,迅速中和溶液中的NH4OH,使反应(1)得以抑制;同时通过添加CaCO3晶种,使新生CaCO3在晶种表面迅速长大,降低其活性,进一步抑制反应(1)的进行。从而有望同时获得高浓度的(NH4)2WO4溶液和高的钨浸出率。
此外,在密闭体系中通入CO2,还可以提高CO2的利用率。
根据本发明的实施例,将粗钨酸铵溶液净化除杂,净化除杂的方法不受特别限制,只要净化后溶液中P、As、Si、Mo、S、Sn、Sb、Ca、Mg、K、Na等杂质的含量满足制备合格APT产品质量要求即可。根据本发明的一个实施例,可以采用沉淀法除去钨酸铵溶液中的杂质,由此制备出钨酸铵精制液。
根据本发明的实施例,可以将钨酸铵精制液采用蒸发结晶法制取APT,蒸发结晶的条件不受特别限制。根据本发明的一个实施例,在95℃下,将钨酸铵溶液蒸发至pH为6.5,经固液分离和产品洗涤后,获得的APT产品纯度符合GB/T 10116-2007中0级品标准。
实施例1:按CaO/WO3分子比为3.3,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣(主要成分为CaCO3)及矿化剂氟化钙进行磨细、混匀后得到生料,氟化钙的加入量为干钨矿物原料量的5.2%(质量百分数),生料粒度≤40μm,然后,在焙烧炉中,空气气氛下,800℃焙烧2.0h,得到熟料。熟料冷却至室温后,用振动磨矿机磨细,熟料粒度≤45μm。称取5.0g磨细后的熟料加入到带通气和机械搅拌装置的反应釜中,同时加入50g-(NH4)2CO3/100g-H2O的碳酸铵溶液50mL并密闭,然后通入CO2气体,控制反应体系的绝对压力为2atm,在80℃下反应5h。反应结束后,浸出矿浆采用真空抽滤,用纯水洗涤滤饼三次。熟料中钨的浸出率为97.15%。
实施例2:按(CaO+FeO)/WO3分子比为4.5,将某黑白钨混合矿(WO3质量百分含量为63.75%,Fe质量百分含量为5.90%)与熟料浸出渣进行磨细、混匀后得到生料,生料粒度≤45μm,然后,在竖炉中,弱还原性气氛下,950℃焙烧3.0h,得到熟料。熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm。称取20.0g熟料加入到带通气和机械搅拌装置的反应釜中,同时加入35g-(NH4)2CO3/100g-H2O的碳酸铵溶液100mL并密闭,然后通入CO2气体,控制反应体系的绝对压力为2atm,在70℃下反应4h。反应结束后,浸出矿浆采用真空抽滤,用纯水洗涤滤饼三次。熟料中钨的浸出率为87.17%。
实施例3:按(CaO+FeO+MnO)/WO3分子比为3.4,将某黑钨矿(WO3质量百分含量为62.40%,Fe质量百分含量为14.08%,Mn质量百分含量为2.25%)与熟料浸出渣及氟化钙进行磨细、混匀后得到生料,氟化钙的加入量为干钨矿物原料量的7%(质量百分数),生料粒度≤40μm,然后,在管式焙烧炉中,中性气氛下,800℃下焙烧6.0h,得到熟料,熟料冷却至室温后,用棒磨机磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,并按照理论量的1.0倍加入碳酸氢铵;将熟料放入浸出设备,在80℃下反应4h。反应结束后,浸出矿浆采用真空抽滤,用纯水洗涤滤饼三次。钨的浸出率为97.13%。然后,将粗钨酸铵溶液净化除杂,净化后溶液采用蒸发结晶析出APT,同时获得氨气和二氧化碳气体,对结晶后的浆液进行液固分离,得到结晶母液和固相,固相经水洗涤后即获得APT产品,APT产品达到国家0级品标准要求;得到的氨气和二氧化碳一起返回到浸出设备,并在补充损失的碳酸铵后循环浸出熟料。
实施例4:按(CaO+FeO)/WO3分子比为3.0,将某黑钨矿(WO3质量百分含量为42.17%,Fe质量百分含量为11.34%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的1.5%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中,弱还原性性气氛下,850℃焙烧5.0h,得到熟料,熟料冷却至室温后,用搅拌磨磨细,熟料粒度≤45μm;浸出设备选择球磨溶出器,内置碳酸铵饱和溶液,并按照理论量的1.1倍加入碳酸氢铵;将熟料放入浸出设备,在40℃下反应4h。反应结束后,浸出矿浆采用真空抽滤,用纯水洗涤滤饼三次。钨的浸出率为97.78%。然后,类似实施例3但补充碳酸氢铵和氨水。
实施例5:按CaO/WO3分子比为6.0,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)、熟料浸出渣和氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的3%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛870℃下焙烧4h,得到熟料,熟料冷却至室温后,用对辊机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.3倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为5%)并密闭,然后通入二氧化碳气体,控制浸出体系的绝对压力为2atm,在30℃下反应5h。反应结束后,浸出矿浆用纯水洗涤滤饼三次。钨的浸出率为98.51%。然后,类似实施例3但补充氨水和CO2。
实施例6:按(CaO+FeO)/WO3分子比为7,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉中性气氛1000℃下焙烧7h,得到熟料,熟料冷却至室温后,用离心磨机磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为35g-(NH4)2CO3/100g-H2O,并按照理论量的1.3倍加入碳酸氢铵;将熟料放入浸出设备,在40℃下反应9h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.99%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例7:按CaO/WO3分子比为7,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤40μm,然后,在焙烧炉中性气氛950℃下焙烧5h,得到熟料,熟料冷却至室温后,用行星磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置饱和碳酸铵和含20g/LWO3的钨酸铵混合溶液,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3质量百分含量为9.5%)并密闭,然后,通入二氧化碳气体,控制浸出体系的绝对压力为3atm,在20℃下反
应6h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为99.01%。然后,类似实施例3但补充氨水和CO2。
实施例8:按CaO/WO3分子比为8,将某钨细泥(WO3质量百分含量为16.22%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤40μm,然后,在焙烧炉还原气氛940℃下焙烧3h,得到熟料,熟料冷却至室温后;浸出设备选择带搅拌的浸出槽,内置饱和碳酸铵和含120g/L WO3的钨酸铵混合溶液,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为10%)并密闭,在30℃下反应4h。反应结束后,浸出矿浆,用纯水洗涤滤饼三次。钨的浸出率为97.51%。然后,类似实施例3但补充氨水和CO2。
实施例9:按(CaO+FeO)/WO3分子比为1.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉中性气氛965℃下焙烧1.5h,得到熟料,熟料冷却至室温后,用对辊机磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为67g-(NH4)2CO3/100g-H2O,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,在18℃下反应6.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为29.30%。
实施例10:按(CaO+FeO)/WO3分子比为1.2,将某黑白钨混合矿(WO3质量百分含量为43.20%,Fe质量百分含量为7.18%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后在焙烧炉中性气氛500℃下焙烧3h,得到熟料,熟料冷却至室温后,用振动磨机磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为50g-(NH4)2CO3/100g-H2O,并按照理论量的1.25倍加入碳酸氢铵;将熟料放入浸出设备,在28℃下反应3.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为9.76%。
实施例11:按CaO/WO3分子比为9,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤200μm,然后,在焙烧炉中性气氛950℃下焙烧4h,得到熟料,熟料冷却至室温后,用振动磨机磨细,熟料粒度≤40μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.1倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为10%)并密闭,在27℃下反应4.5h。反应结束后,浸出矿浆压滤,用纯水洗涤滤饼三次。钨的浸出率为89.05%。然后,类似实施例3但补充氨水和CO2。
实施例12:按CaO/WO3分子比为2.3,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的1%(质量百分数),生料粒度≤100μm,然后,在焙烧炉中性气氛845℃下焙烧2.5h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为5.9%)并密闭,然后,通入二氧化碳气体,控制浸出体系的绝对压力为2.5atm,在27℃下反应4.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为73.65%。然后,类似实施例3但补充氨水和碳酸氢铵。
实施例13:按CaO/WO3分子比为3.6,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉中性气氛870℃下焙烧1h,得到熟料,熟料冷却至室温后,用气流粉碎机磨细,熟料粒度≤74μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为20%)并密闭,在32℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为96.15%。然后,类似实施例3但补充碳酸氢铵。
实施例14:按(CaO+FeO)/WO3分子比为4.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的0.5%(质量百分数),生料粒度≤50μm,然后,在焙烧炉中性气氛920℃下焙烧2h,得到熟料,熟料冷却至室温后,用搅拌磨机磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在38℃下反应2h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为98.22%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例15:按(CaO+FeO)/WO3分子比为3.4,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉中性气氛960℃下焙烧2h,得到熟料,熟料冷却至室温后,用棒磨机磨细,熟料粒度≤200μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料
放入浸出设备,在38℃下反应5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为98.35%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例16:按(CaO+FeO)/WO3分子比为4.1,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤61μm,然后,在焙烧炉氧化性气氛970℃下焙烧2h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,在55℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为97.31%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例17:按CaO/WO3分子比为6.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤53μm,然后,在焙烧炉中性气氛990℃下焙烧0.5h,得到熟料,熟料冷却至室温后,用行星磨机磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.5倍加入碳酸氢铵;将熟料放入浸出设备,在62℃下反应2h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼5次。钨的浸出率为96.78%。然后,类似实施例3但补充碳酸铵和氨水,APT产品达到国家0级品标准要求。
实施例18:按(CaO+FeO)/WO3分子比为4.7,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤74μm,然后,在焙烧炉中性气氛980℃下焙烧2h,得到熟料,熟料冷却至室温后,用高压盘磨机磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.6倍加入碳酸氢铵;将熟料放入浸出设备,在75℃下反应3.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为97.01%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例19:按CaO/WO3分子比为3.8,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的0.5%(质量百分数),生料粒度≤40μm,然后,在焙烧炉中性气氛880℃下焙烧1h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为8.2%)并密闭,然后通入二氧化碳气体,控制浸出体系的绝对压力为3atm,在32℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.15%。然后,类似实施例3但补充氨水和CO2。
实施例20:按CaO/WO3分子比为3.8,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的5%(质量百分数),生料粒度≤30μm,然后,在焙烧炉中性气氛860℃下焙烧1h,得到熟料,熟料冷却至室温后,用塔式磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置饱和碳酸铵和含60g/L WO3的钨酸铵混合溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为15%)并密闭,然后通入二氧化碳气体,控制浸出体系的绝对压力为1.2atm,在35℃下反应6h。反应结束后,浸出矿浆压滤,用纯水洗涤滤饼三次。钨的浸出率为98.03%。然后,类似实施例3但补充氨水、CO2和碳酸铵。
实施例21:按CaO/WO3分子比为2.0,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤36μm,然后,在焙烧炉还原性气氛880℃下焙烧1h,得到熟料,熟料冷却至室温后,用振动磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为10.0%)并密闭,然后通入二氧化碳气体,控制浸出体系的绝对压力为1.5atm,在32℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为42.75%。然后,类似实施例3但补充碳酸氢铵、氨水和CO2。
实施例22:按CaO/WO3分子比为1.8,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉中性气氛880℃下焙烧1h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为7.4%)并密闭,然后,通入二氧化碳气体,控制浸出体系的绝对压力为1.9atm,在32℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为38.35%。然后,类似实施例3但补充氨水和CO2。
实施例23:按(CaO+FeO)/WO3分子比为1.5,将某白钨矿(WO3质量百分含量为52.33%,Fe
质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤33μm,然后,在焙烧炉中性气氛965℃下焙烧5h,得到熟料,熟料冷却至室温后,用振动磨机磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为80g-(NH4)2CO3/100g-H2O,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,在20℃下反应6.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为22.96%。然后,类似实施例3。
实施例24:按(CaO+FeO)/WO3分子比为2.9,将某黑白钨混合矿(WO3质量百分含量为43.20%,Fe质量百分含量为7.18%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的2%(质量百分数),生料粒度≤30μm,然后,在焙烧炉中性气氛850℃下焙烧3h,得到熟料,熟料冷却至室温后,用对辊机磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为80g-(NH4)2CO3/100g-H2O,并按照理论量的1.25倍加入碳酸氢铵;将熟料放入浸出设备,在28℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为95.71%。然后,类似实施例3但补充碳酸铵、碳酸氢铵和氨水。
实施例25:按CaO/WO3分子比为4,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤28μm,然后,在焙烧炉氧化性气氛950℃下焙烧4h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为20%)并密闭,在27℃下反应4.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.35%。然后,类似实施例3但补充氨水。
实施例26:按CaO/WO3分子比为2.3,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的4.5%(质量百分数),生料粒度≤41μm,然后,在焙烧炉中性气氛845℃下焙烧2.5h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤83μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为9.8%)并密闭,在37℃下反应4.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为68.65%。然后,类似实施例3但补充碳酸铵、氨水和CO2。
实施例27:按(CaO+FeO)/WO3分子比为4.8,将某白钨矿(WO3质量百分含量为52.27%,Fe质量百分含量为5.86%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的2.5%(质量百分数),生料粒度≤61μm,然后,在焙烧炉中性气氛870℃下焙烧1h,得到熟料,熟料冷却至室温后,用棒磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,在32℃下反应8.0h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为97.10%。然后,类似实施例3但补充氨水和CO2。
实施例28:按(CaO+FeO+MnO)/WO3分子比为4.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与菱锰矿和石灰石进行磨细混匀后得到生料,生料粒度≤14μm,然后,在焙烧炉中性气氛920℃下焙烧2h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在43℃下反应5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为98.42%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例29:按(CaO+FeO)/WO3分子比为4.9,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤42μm,然后,在焙烧炉中性气氛960℃下焙烧2h,得到熟料,熟料冷却至室温后,用行星磨磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在38℃下反应5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为97.35%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例30:按(CaO+MnO)/WO3分子比为4.6,将某白钨矿(WO3质量百分含量为60.94%)与菱锰矿和熟料浸出渣进行磨细混匀后得到生料,生料粒度≤44μm,然后,在焙烧炉中性气氛980℃下焙烧1.5h,得到熟料,熟料冷却至室温后,用搅拌磨磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.5倍加入碳酸氢铵;将熟料放入浸出设备,在50℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼4次。钨的浸出率为97.99%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例31:按CaO/WO3分子比为4.3,将某白钨矿(WO3质量百分含量为60.94%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤48μm,然后,在焙烧炉中性气氛970℃下焙烧2h,
得到熟料,熟料冷却至室温后,用棒磨机磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在55℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼。钨的浸出率为97.74%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例32:按(CaO+FeO)/WO3分子比为4.9,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤38μm,然后,在焙烧炉氧化气氛990℃下焙烧1h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.5倍加入碳酸氢铵;将熟料放入浸出设备,在62℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼5次。钨的浸出率为97.78%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例33:按CaO/WO3分子比为5.1,将某白钨矿(WO3质量百分含量为60.94%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤63μm,然后,在焙烧炉中性气氛980℃下焙烧2h,得到熟料,熟料冷却至室温后,用搅拌磨磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.3倍加入碳酸氢铵;将熟料放入浸出设备,在75℃下反应0.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为97.51%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例34:按(CaO+MnO)/WO3分子比为5.1,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与菱锰矿和熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的6.0%(质量百分数),生料粒度≤36μm,然后,在焙烧炉中性气氛880℃下焙烧1h,得到熟料,熟料冷却至室温后,用搅拌磨磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.5倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为5.0%)并密闭,在32℃下反应3.8h。反应结束后,浸出矿浆压滤,用纯水洗涤滤饼三次。钨的浸出率为98.15%。然后,类似实施例3但补充碳酸铵、碳酸氢铵、氨水和CO2。
实施例35:按(CaO+MnO)/WO3分子比为5.1,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与菱锰矿和熟料浸出渣进行磨细混匀后得到生料,生料粒度≤36μm,然后,在焙烧炉中性气氛880℃下焙烧1h,得到熟料,熟料冷却至室温后,用搅拌磨磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.5倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为5.0%)并密闭,在32℃下反应3.8h。反应结束后,浸出矿浆压滤,用纯水洗涤滤饼三次。钨的浸出率为86.23%。然后,类似实施例3但补充碳酸铵、碳酸氢铵、氨水和CO2。
实施例36:按CaO/WO3分子比为2.5,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的4.5%(质量百分数),生料粒度≤37μm,然后,在焙烧炉还原性气氛880℃下焙烧1h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤53μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.15倍加入碳酸氢铵;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为4.1%)并密闭,然后,通入二氧化碳气体,控制浸出体系的绝对压力为1.3atm,在32℃下反应9h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为74.75%。然后,类似实施例3但补充碳酸氢铵、氨水和CO2。
实施例37:按CaO/WO3分子比为2.2,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与石灰石进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的1.5%(质量百分数),生料粒度≤24μm,然后,在焙烧炉还原性气氛880℃下焙烧3h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液;将熟料放入浸出设备,在32℃下反应8.0h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为55.45%。然后,类似实施例3但补充氨水和CO2。
实施例38:按(CaO+FeO)/WO3分子比为10,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与菱铁矿和熟料浸出渣进行磨细混匀后得到生料,生料粒度≤38μm,然后,在焙烧炉中性气氛950℃下焙烧1h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为58g-(NH4)2CO3/100g-H2O,并按照理论量的1.3倍加入碳酸氢铵;将熟料放入浸出设备,在40℃下反应9h。反应结束后,浸出矿浆压滤,用纯水洗涤滤饼三次。钨的浸出率为96.93%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例39:按CaO/WO3分子比为5.1,将某白钨矿(WO3质量百分含量为49.53%,Fe质量
百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的1.0%(质量百分数),生料粒度≤33μm,然后,在焙烧炉中性气氛895℃下焙烧8h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.9倍加入碳酸氢铵;将熟料放入浸出设备,在20℃下反应6h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为95.01%。然后,类似实施例3但补充氨水和CO2。
实施例40:按CaO/WO3分子比为3.9,将某钨细泥(WO3质量百分含量为16.22%)与石灰石进行磨细混匀后得到生料,生料粒度≤40μm,然后,在焙烧炉还原性气氛940℃下焙烧3h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为12%)并密闭,在50℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为92.31%。然后,类似实施例3但补充氨水和CO2。
实施例41:按(CaO+FeO)/WO3分子比为6.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与石灰石进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的0.7%(质量百分数),生料粒度≤30μm,然后,在焙烧炉中性气氛965℃下焙烧1.5h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为67g-(NH4)2CO3/100g-H2O,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,在10℃下反应20.0h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为91.96%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例42:按(CaO+FeO)/WO3分子比为3.6,将某黑白钨混合矿(WO3质量百分含量为43.20%,Fe质量百分含量为7.18%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的2.6%(质量百分数),生料粒度≤25μm,然后,在焙烧炉中性气氛850℃下焙烧3h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为70g-(NH4)2CO3/100g-H2O,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在40℃下反应3.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.76%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例43:按CaO/WO3分子比为10,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤28μm,然后,在焙烧炉中性气氛845℃下焙烧4h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤74μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为28%)并密闭,在27℃下反应4.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为96.01%。然后,类似实施例3但补充碳酸铵、氨水和CO2。
实施例44:按CaO/WO3分子比为3.5,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的5.5%(质量百分数),生料粒度≤40μm,然后,在焙烧炉中性气氛845℃下焙烧10h,得到熟料,熟料冷却至室温后,用对辊机磨细,熟料粒度≤150μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为7.5%)并密闭,在27℃下反应4.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.49%。然后,类似实施例3但补充氨水和CO2。
实施例45:按CaO/WO3分子比为4.5,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉中性气氛1050℃下焙烧6h,得到熟料,熟料冷却至室温后,用棒磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为9.1%)并密闭,在32℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为97.15%。然后,类似实施例3但补充碳酸氢铵、氨水和CO2。
实施例46:按(CaO+FeO)/WO3分子比为4.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的6%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛995℃下焙烧0.5h,得到熟料,熟料冷却至室温后,用雷蒙磨磨细,熟料粒度≤8μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在38℃下反应5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为97.22%。然后,类似实施例
3,APT产品达到国家0级品标准要求。
实施例47:按(CaO+FeO)/WO3分子比为5.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的2%(质量百分数),生料粒度≤45μm,然后,在焙烧炉还原性气氛960℃下焙烧2h,得到熟料,熟料冷却至室温后,用气流粉碎机磨细,熟料粒度≤20μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在38℃下反应5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为98.16%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例48:按(CaO+FeO)/WO3分子比为4.2,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的3.5%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛850℃下焙烧0.5h,得到熟料,熟料冷却至室温后,用雷蒙磨磨细,熟料粒度≤8μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.5倍加入碳酸氢铵;将熟料放入浸出设备,在50℃下反应4h。反应结束后,浸出矿浆压滤,用纯水洗涤滤饼4次。钨的浸出率为98.33%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例49:按(CaO+FeO)/WO3分子比为4.1,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤53μm,然后,在焙烧炉中性气氛930℃下焙烧8h,得到熟料,熟料冷却至室温后,用悬辊粉碎机磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.1倍加入碳酸氢铵;将熟料放入浸出设备,在25℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为94.22%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例50:按CaO/WO3分子比为5.6,将某白钨矿(WO3质量百分含量为60.94%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的2.5%(质量百分数),生料粒度≤53μm,然后,在焙烧炉中性气氛910℃下焙烧1h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.5倍加入碳酸氢铵;将熟料放入浸出设备,在62℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼5次。钨的浸出率为98.78%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例51:按(CaO+FeO)/WO3分子比为4.7,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的2.8%(质量百分数),生料粒度≤74μm,然后,在焙烧炉中性气氛900℃下焙烧2h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.6倍加入碳酸氢铵;将熟料放入浸出设备,在75℃下反应1.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为95.01%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例52:按CaO/WO3分子比为3.8,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的3.3%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛880℃下焙烧1h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为8.0%)并密闭,在50℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为96.15%。然后,类似实施例3但补充氨水和CO2。
实施例53:按CaO/WO3分子比为4.8,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的7%(质量百分数),生料粒度≤40μm,然后,在焙烧炉中性气氛810℃下焙烧1h,得到熟料,熟料冷却至室温后,用行星磨磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为5.5%)并密闭,在45℃下反应6h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.63%。然后,类似实施例3但补充氨水和CO2。
实施例54:按CaO/WO3分子比为3.0,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的5%(质量百分数),生料粒度≤96μm,然后,在焙烧炉还原性气氛880℃下焙烧1h,得到熟料,熟料冷却至室温后,用搅拌磨磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳
酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为3.5%)并密闭,在32℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为96.75%。然后,类似实施例3但补充氨水和CO2。
实施例55:按CaO/WO3分子比为12,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的1.5%(质量百分数),生料粒度≤36μm,然后,在焙烧炉中性气氛750℃下焙烧5h,得到熟料,熟料冷却至室温后,用对辊机磨细,熟料粒度≤100μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,在32℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为86.35%。
实施例56:按(CaO+FeO)/WO3分子比为7,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与石灰石进行磨细混匀后得到生料,生料粒度≤106μm,然后,在焙烧炉中性气氛1000℃下焙烧7h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为35g-(NH4)2CO3/100g-H2O,并按照理论量的1.3倍加入碳酸氢铵;将熟料放入浸出设备,在40℃下反应9h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为95.99%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例57:按CaO/WO3分子比为7,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉中性气氛1200℃下焙烧5h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,在20℃下反应6h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为78.01%。
实施例58:按CaO/WO3分子比为8,将某钨细泥(WO3质量百分含量为16.22%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤96μm,然后,在焙烧炉还原气氛1400℃下焙烧3h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为6%)并密闭,在30℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为81.51%。然后,类似实施例3但补充碳酸铵、碳酸氢铵、氨水和CO2。
实施例59:按(CaO+FeO)/WO3分子比为3.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉中性气氛965℃下焙烧8h,得到熟料,熟料冷却至室温后,用离心磨机磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为20g-(NH4)2CO3/100g-H2O,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,在18℃下反应6.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为92.96%。然后,类似实施例3。
实施例60:按(CaO+FeO)/WO3分子比为3.2,将某黑白钨混合矿(WO3质量百分含量为43.20%,Fe质量百分含量为7.18%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的1.5%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛850℃下焙烧3h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,,并按照理论量的1.25倍加入碳酸氢铵;将熟料放入浸出设备,在28℃下反应3.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为96.76%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例61:按CaO/WO3分子比为9,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的1%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛950℃下焙烧4h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤96μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为5.9%)并密闭,在47℃下反应4.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.15%。然后,类似实施例3但补充氨水和CO2。
实施例62:按CaO/WO3分子比为3.2,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的2.8%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛845℃下焙烧5h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵溶液,碳酸铵浓度为40g-(NH4)2CO3/100g-H2O;将熟料放入浸出设备,同时加
入氨水(使浸出溶液中NH3的质量百分含量为4%)并密闭,在45℃下反应4.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为97.65%。然后,类似实施例3但补充氨水和CO2。
实施例63:按CaO/WO3分子比为3.8,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的1.2%(质量百分数),生料粒度≤120μm,然后,在焙烧炉中性气氛870℃下焙烧3h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵溶液,,碳酸铵浓度为45g-(NH4)2CO3/100g-H2O;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为7.9%)并密闭,在5℃下反应15h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为93.15%。然后类似实施例3但补充碳酸铵、氨水和CO2。
实施例64:按(CaO+FeO)/WO3分子比为4.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的5.4%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛750℃下焙烧4h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在38℃下反应5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为97.22%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例65:按(CaO+FeO)/WO3分子比为3.4,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的3%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛760℃下焙烧15h,得到熟料,熟料冷却至室温后,用棒磨机磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在38℃下反应5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为97.35%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例66:按(CaO+FeO)/WO3分子比为4.2,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉中性气氛980℃下焙烧8h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的4倍加入碳酸氢铵;将熟料放入浸出设备,在50℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼4次。钨的浸出率为96.33%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例67:按(CaO+FeO)/WO3分子比为4.1,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与石灰石及萤石进行磨细混匀后得到生料,萤石的加入量为干钨矿物原料量的6%(质量百分数),生料粒度≤48μm,然后,在焙烧炉中性气氛970℃下焙烧2h,得到熟料,熟料冷却至室温后,用搅拌磨机磨细,熟料粒度≤40μm;浸出设备选择搅拌浸出器,内置碳酸铵溶液,碳酸铵浓度为25g-(NH4)2CO3/100g-H2O,并按照理论量的1.4倍加入碳酸氢铵;将熟料放入浸出设备,在80℃下反应0.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为96.36%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例68:按(CaO+FeO)/WO3分子比为6.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤53μm,然后,在焙烧炉中性气氛990℃下焙烧8h,得到熟料,熟料冷却至室温后,用棒磨机磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,并按照理论量的3倍加入碳酸氢铵;将熟料放入浸出设备,在62℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼5次。钨的浸出率为97.70%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例69:按(CaO+FeO)/WO3分子比为4.7,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣及萤石进行磨细混匀后得到生料,萤石的加入量为干钨矿物原料量的4%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛980℃下焙烧2h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤40μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.6倍加入碳酸氢铵;将熟料放入浸出设备,在75℃下反应3.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为97.01%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例70:按CaO/WO3分子比为3.2,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿
物原料量的2.5%(质量百分数),生料粒度≤36μm,然后,在焙烧炉中性气氛880℃下焙烧1h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为6.7%)并密闭,在90℃下反应0.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为93.15%。然后类似实施例3但补充氨水和CO2。
实施例71:按CaO/WO3分子比为3.8,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的3.6%(质量百分数),生料粒度≤90μm,然后,在焙烧炉中性气氛860℃下焙烧1h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.1倍加入碳酸氢铵;将熟料放入浸出设备,在45℃下反应6h。反应结束后,浸出矿浆压滤,用纯水洗涤滤饼三次。钨的浸出率为97.09%。然后,类似实施例3但补充碳酸铵、碳酸氢铵、氨水和CO2。
实施例72:按CaO/WO3分子比为3.1,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的4.8%(质量百分数),生料粒度≤45μm,然后,在焙烧炉还原性气氛880℃下焙烧1h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为7.5%)并密闭,在32℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为97.75%。然后,类似实施例3但补充氨水和CO2。
实施例73:按CaO/WO3分子比为3.8,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的0.7%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛880℃下焙烧9h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为8.6%)并密闭,在32℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.65%。然后类似实施例3但补充碳酸铵、氨水和CO2。
实施例74:按CaO/WO3分子比为3.7,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的4.5%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中,空气气氛下,800℃焙烧2.0h,得到熟料。熟料冷却至室温后,用振动磨矿机磨细,熟料粒度≤45μm。称取25.0g磨细后的熟料加入到带通气和机械搅拌装置的反应釜中,同时加入60g-(NH4)2CO3/100g-H2O的碳酸铵溶液100mL并密闭,然后,通入CO2气体,控制反应体系的绝对压力为2atm,在80℃下反应4h。反应结束后,浸出矿浆采用真空抽滤,用纯水洗涤滤饼三次。熟料中钨的浸出率为97.25%。
实施例75:按(CaO+FeO)/WO3分子比为4.5,将某黑白钨混合矿(WO3质量百分含量为63.75%,Fe质量百分含量为5.90%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的0.5%(质量百分数),生料粒度≤45μm,然后,在竖炉中,弱还原性气氛下,1000℃焙烧3.0h,得到熟料。熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm。称取30.0g磨细后的熟料加入到带通气和机械搅拌装置的反应釜中,同时加入45g-(NH4)2CO3/100g-H2O的碳酸铵溶液100mL并密闭,然后通入CO2气体,控制反应体系的绝对压力为2atm,在70℃下反应4h。反应结束后,浸出矿浆采用真空抽滤,用纯水洗涤滤饼三次。熟料中钨的浸出率为95.17%。
实施例76:按(CaO+FeO)/WO3分子比为3.8,将某黑钨矿(WO3质量百分含量为60.40%,Fe质量百分含量为15.08%)与熟料浸出渣及氟化钙进行磨细、混匀后得到生料,氟化钙的加入量为干钨矿物原料量的3%(质量百分数),生料粒度≤45μm,然后,在管式焙烧炉中,中性气氛下,800℃下焙烧6.0h,得到熟料,熟料冷却至室温后,用棒磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在80℃下反应4h。反应结束后,浸出矿浆采用真空抽滤,用纯水洗涤滤饼三次。钨的浸出率为97.13%。然后,类似实施例3补充损失的碳酸铵。
实施例77:按(CaO+FeO)/WO3分子比为3.5,将某黑钨矿(WO3质量百分含量为42.17%,Fe质量百分含量为11.34%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的0.9%(质量百分数),生料粒度≤45μm。然后,在焙烧炉中,弱还原性性气氛下,950℃焙烧5.0h,得到熟料,熟料冷却至室温后,用搅拌磨磨细,熟料粒度≤40μm;浸出设备选择球磨溶出器,内置碳酸铵饱和溶液,并按照理论量的1.1倍加入碳酸氢铵;将熟料放入浸出设
备,在75℃下反应4h。反应结束后,浸出矿浆采用真空抽滤,用纯水洗涤滤饼三次。钨的浸出率为96.78%。然后,类似实施例3但补充碳酸氢铵。
实施例78:按CaO/WO3分子比为6.0,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的2.4%(质量百分数),生料粒度≤30μm,然后在焙烧炉中性气氛870℃下焙烧4h,得到熟料,熟料冷却至室温后,用行星磨磨细,熟料粒度≤74μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为6.5%)并密闭,在30℃下反应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.09%。然后类似实施例3但补充氨水和CO2。
实施例79:按(CaO+FeO)/WO3分子比为7,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤25μm,然后,在焙烧炉中性气氛1000℃下焙烧7h,得到熟料,熟料冷却至室温后,用振动磨机磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为60g-(NH4)2CO3/100g-H2O,并按照理论量的1.3倍加入碳酸氢铵;将熟料放入浸出设备,在40℃下反应9h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.03%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例80:按CaO/WO3分子比为3.0,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的3.2%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛950℃下焙烧5h,得到熟料,熟料冷却至室温后,用雷蒙磨机磨细,熟料粒度≤8μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为10.0%)并密闭,控制浸出体系的绝对压力为1.0atm,在20℃下反应12h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为96.20%。然后,类似实施例3但补充碳酸氢铵、氨水和CO2。
实施例81:按CaO/WO3分子比为8,将某钨细泥(WO3质量百分含量为16.22%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉还原气氛950℃下焙烧3h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为6.3%)并密闭,在35℃下反应15h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为91.51%。然后,补充氨水和CO2。
实施例82:按(CaO+FeO)/WO3分子比为3.6,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的4.1%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛965℃下焙烧1.5h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤60μm;浸出设备选择球磨浸出器,内置碳酸铵-钨酸铵混合溶液,碳酸铵浓度为45g-(NH4)2CO3/100g-H2O,溶液中WO3浓度为40g/L,并按照理论量的2倍加入碳酸氢铵;将熟料放入浸出设备,在18℃下反应6.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为97.96%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例83:按(CaO+FeO)/WO3分子比为3.3,将某黑白钨混合矿(WO3质量百分含量为43.20%,Fe质量百分含量为7.18%),与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的2.2%(质量百分数),生料粒度≤45μm,然后在焙烧炉中性气氛850℃下焙烧3h,得到熟料,熟料冷却至室温后,用棒磨机磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵溶液,碳酸铵浓度为40g-(NH4)2CO3/100g-H2O,并按照理论量的1.25倍加入碳酸氢铵;将熟料放入浸出设备,在42℃下反应20h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.76%。然后,类似实施例3但补充碳酸铵和碳酸氢铵,APT产品达到国家0级品标准要求。
实施例84:按CaO/WO3分子比为9,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的0.55%(质量百分数),生料粒度≤30μm,然后,在焙烧炉中性气氛950℃下焙烧4h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置饱和碳酸铵和含60g/L WO3的钨酸铵混合溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为9.1%)并密闭,在37℃下反应4.5h。反应结束后,浸出矿浆压滤,用纯水洗涤滤饼三次。钨的浸出率为98.72%。然后类似实施例3但补充氨水和CO2。
实施例85:按CaO/WO3分子比为2.7,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤45μm,然后,在焙烧炉中性气氛845℃下焙烧2.5h,得到熟料,熟料冷却至室温后,用悬辊粉碎机磨细,熟料粒度≤74μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在45℃下反应4.5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为81.65%。然后类似实施例3但补充氨水和CO2。
实施例86:按CaO/WO3分子比为3.8,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的1.5%(质量百分数),生料粒度≤45μm,然后,在焙烧炉中性气氛870℃下焙烧1h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带球磨的浸出槽,内置过饱和碳酸铵浆液,碳酸铵浓度为100g(NH4)2CO3/100g H2O;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为6.5%)并密闭,在52℃下反应3.8h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.25%。然后类似实施例3但补充碳酸铵、碳酸氢铵、氨水和CO2。
实施例87:按(CaO+FeO)/WO3分子比为4.5,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与石灰石及萤石进行磨细混匀后得到生料,萤石的加入量为干钨矿物原料量的2.6%(质量百分数),生料粒度≤45μm,然后,在焙烧炉还原性气氛920℃下焙烧2h,得到熟料,熟料冷却至室温后,用雷蒙磨机磨细,熟料粒度≤8μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在38℃下反应5h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼2次。钨的浸出率为98.12%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例88:按(CaO+FeO)/WO3分子比为3.4,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与实施例86中熟料浸出后的渣(主要成分为CaCO3)及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的4.1%(质量百分数),生料粒度≤100μm,然后,在焙烧炉中性气氛960℃下焙烧2h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤45μm;浸出设备选择搅拌浸出器,内置碳酸铵饱和溶液,并按照理论量的1.2倍加入碳酸氢铵;将熟料放入浸出设备,在50℃下反应3h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼5次。钨的浸出率为98.39%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例89:按(CaO+FeO)/WO3分子比为4.2,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与实施例88中熟料浸出后的渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的0.2%(质量百分数),生料粒度≤74μm,然后,在焙烧炉中性气氛980℃下焙烧1.5h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤85μm;浸出设备选择球磨浸出器,内置过饱和碳酸铵浆液,碳酸铵浓度为120g(NH4)2CO3/100g H2O,并按照理论量的1.5倍加入碳酸氢铵;将熟料放入浸出设备,在70℃下反应6h。反应结束后,浸出矿浆压滤,用纯水洗涤滤饼4次。钨的浸出率为97.23%。然后,类似实施例3但补充碳酸铵和碳酸氢铵,APT产品达到国家0级品标准要求。
实施例90:按(CaO+FeO)/WO3分子比为7,将某白钨矿(WO3质量百分含量为52.33%,Fe质量百分含量为2.04%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤80μm,然后,在焙烧炉中性气氛1000℃下焙烧7h,得到熟料,熟料冷却至室温后,用振动磨磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液,并按照理论量的1.3倍加入碳酸氢铵;将熟料放入浸出设备,在40℃下反应24h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为98.66%。然后,类似实施例3,APT产品达到国家0级品标准要求。
实施例91:按CaO/WO3分子比为4,将某白钨矿(WO3质量百分含量为49.53%,Fe质量百分含量为0.43%)与熟料浸出渣进行磨细混匀后得到生料,生料粒度≤53μm,然后,在焙烧炉中性气氛950℃下焙烧10h,得到熟料,熟料冷却至室温后,用球磨机磨细,熟料粒度≤45μm;浸出设备选择带搅拌的浸出槽,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为13.0%)并密闭,在40℃下反应20h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为99.01%。然后,类似实施例3但补充氨水和CO2。
实施例92:按CaO/WO3分子比为8,将某钨细泥(WO3质量百分含量为16.22%)与熟料浸出渣及氟化钙进行磨细混匀后得到生料,氟化钙的加入量为干钨矿物原料量的6.5%(质量百分数),生料粒度≤45μm,然后,在焙烧炉还原气氛750℃下焙烧0.5h,得到熟料,熟料冷却至室温后,用离心磨机磨细,熟料粒度≤45μm;浸出设备选择球磨浸出器,内置碳酸铵饱和溶液;将熟料放入浸出设备,同时加入氨水(使浸出溶液中NH3的质量百分含量为8.5%)并密闭,在45℃下反
应4h。反应结束后,浸出矿浆抽滤,用纯水洗涤滤饼三次。钨的浸出率为94.51%。然后,类似实施例3但补充碳酸铵、碳酸氢铵、氨水和CO2。
本发明人多年的反复探索和实践表明,本领域的技术人员没有动机去考虑本发明的技术构思,不存在采用“公知常识”或“惯用手段”的问题。退一步说,即使有了构思,涉及的多个因素往往都是相互制约的,相互影响的,并不是相互独立的,即使采用正交设计等现代化科学手段,仍然有无穷的可能组合,而且不能预测出足够优异的技术方案,“有限次的实验”不可能得到各因素的适当取值,足够优异的技术方案更不是“显而易见”的。
本发明的以上众多实施例并不是对本发明的限定。本领域的技术人员可以理解,在不偏离本发明的精神和构思的前提下,任何对本发明技术方案的细节和形式进行的修改、补充、完善和替换,均在所附权利要求书的保护范围内。
Claims (10)
- 一种钨矿物原料的冶金工艺,其特征在于,采用有助于形成局部工艺循环的一种或多种弱碱浸出剂(取代现有技术强碱或强酸浸出剂),其浸出液在蒸发结晶过程中产生两种或两种以上的气体,各气体又可以重新参与合成该浸出剂,结晶后的分离洗涤液同样作为浸出剂循环使用;以及采用一转型配料,其通过与钨矿物原料发生化学反应,可使得钨元素改含在容易被所述弱碱浸出剂溶解的中间物质中,而浸出渣中也含有转型配料元素,以便于至少部分浸出渣可以作为转型配料循环使用,为此,该工艺包含多个闭路循环,全程无废水排放。
- 如权利要求1所述的冶金工艺,其特征在于,该工艺包括以下步骤:在钨矿物原料中添加转型配料(优选地,还添加矿化剂),磨碎、混合均匀,配制成生料后焙烧,使得钨元素改含在容易被所述浸出剂浸出的中间物质中;在配料环节设置回收至少部分浸出渣的手段;采用选定的浸出剂对中间物质进行浸出,在该浸出环节设置浸出剂反应气体的回收手段、结晶浆液分离洗涤液的回收手段、渣相洗涤液的回收手段、以及按照实际需要补充浸出剂的手段;对浸出浆液进行固液分离,以得到含钨元素的粗溶液和含配料元素的浸出渣,对渣相洗涤,洗涤液反馈至熟料浸出环节(第I闭环),根据实际需要,取至少部分浸出渣作为配料反馈,以重复使用配料(第II闭环)(若浸出渣有剩余部分,则堆存);对含钨元素的粗溶液进行至少一级净化除杂(优选地,最后一级可加设抽风措施);对净化后的溶液进行蒸发结晶,以析出含钨元素的中间产品;同时,将释放出的气体返回至浸出环节(第III闭环),而蒸发出的水反馈至浸出浆液的固液分离环节(第IV闭环);对结晶后的浆液进行液固分离,以得到结晶母液和固相,固相经水和/或铵盐溶液洗涤,烘干后即获得含钨元素的最终产品(优选地对固相进行再次溶解和结晶,以得到纯度更高的最终产品);而结晶母液也返回至熟料浸出环节(第V闭环)。
- 根据权利要求1所述的冶金工艺,其特征在于,所述钨矿物原料包括白钨矿、黑钨矿、黑白钨混合矿、和/或钨细泥。
- 根据权利要求1所述的冶金工艺,其特征在于,所述转型包括将钨矿物原料、配料磨细、混合均匀,以制备生料;对生料进行焙烧,以获得熟料(优选将熟料进行破碎、磨细)。
- 根据权利要求1所述的冶金工艺,其特征在于,所述弱碱为碳酸铵、碳酸氢铵、氨水、氨水+CO2气体,以及它们的任意混合物,和/或它们与钨酸铵的任意混合物。
- 根据权利要求1所述的冶金工艺,其特征在于,还包括下列附加技术特征至少其中之一:结晶浆液经液固分离和/或洗涤后,结晶母液和洗液与收集的氨气和二氧化碳混合后(或者分别),反馈至熟料的浸出装置,固体则或经洗涤烘干后制得产品APT,或进入下一级溶解、结晶、提纯子系统;所述配料为含CaCO3的物质,其加入量按生料中CaO/WO3或(CaO+FeO)/WO3或(CaO+MnO)/WO3或(CaO+FeO+MnO)/WO3分子比至少为1.0计,优选为1.5-6.0,更优选为3.0-4.0,更优选为3.3-3.6;所述生料粒度不受特别限制,优选为不大于200μm,更优选为不大于100μm,更优选为不大于40μm;生料焙烧的温度为不低于500℃,优选为800-1050℃,更优选为850-950℃;以及生料焙烧的时间为0.5-8.0h,优选为1.0-3.0h,更优选为2.0h。
- 根据权利要求1所述的冶金工艺,其特征在于,对于白钨矿原料,焙烧气氛不受特别限制,优选为中性或氧化性气氛;对于黑钨矿、黑白钨混合矿和/或钨细泥原料,焙烧气氛为中性或还原性气氛,优选为中性气氛。
- 根据权利要求1所述的冶金工艺,其特征在于,熟料的粒度不受特别限制,优选为不大于200μm,再优选为不大于74μm,再优选为不大于45μm。
- 根据权利要求1所述的冶金工艺,其特征在于,还包括下列附加技术特征至少其中之一:浸出体系中的CO2一部分来自生料焙烧过程所产生的炉(窑)气或者是商品CO2,另一部分来自钨酸铵溶液蒸发结晶过程所产生的CO2,CO2可在浸出过程中通入,也可以在浸出前通入;浸出初始体系中碳酸铵浓度大于20g-(NH4)2CO3/100g-H2O,优选为该体系下其饱和溶液的 浓度;碳酸氢铵则以溶液或固体的形式加入,碳酸氢铵的加入量不受特别限制,优选为不少于使熟料中的钙转化为CaCO3所需量(理论量)的1.0倍,更优选为理论量的1.1-1.4倍;氨水的加入量也不受特别限制,优选地,浸出初始体系中NH3的质量百分含量为0-28%,更优选为5-20%,更优选为5-10%;以及钨酸铵浓度无特别限制,只要能确保熟料中钨充分浸出后所得溶液中的钨酸铵浓度不超过该体系下的平衡浓度即可。
- 根据权利要求1所述的冶金工艺,其特征在于,还包括下列附加技术特征至少其中之一:熟料的浸出过程在密闭体系中进行,以碳酸铵体系、碳酸铵-碳酸氢铵体系、碳酸铵-氨水体系、碳酸铵-碳酸氢铵-钨酸铵体系、碳酸铵-氨水-钨酸铵体系和碳酸铵-钨酸铵体系浸出熟料时,反应体系的绝对压力不受特别限制;以碳酸铵-CO2体系、碳酸铵-碳酸氢铵-CO2体系、碳酸铵-氨水-CO2体系、碳酸铵-钨酸铵-CO2体系、碳酸铵-氨水-钨酸铵-CO2体系和碳酸铵-碳酸氢铵-钨酸铵-CO2体系浸出熟料时,需控制反应体系的绝对压力不小于1atm,优选为2atm;浸出温度不低于5℃,优选为10-80℃,更优选为20-70℃,更优选为30-50℃;浸出时间优选为0.5-8.0h,更优选地浸出时间为2-5h(浸出时间不受特别限制,只要能确保熟料中钨能充分浸出即可);以及净化除杂过程包括除钼、磷、锡、砷、硅、铁、钠、钾、铋、锑、钙、镁中的至少其中之一。
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CN109824064B (zh) * | 2019-03-25 | 2020-02-07 | 中南大学 | 从钨酸钠浸出液中回收碳酸钠的方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19724183A1 (de) * | 1996-07-05 | 1998-01-08 | Starck H C Gmbh Co Kg | Verfahren zur Herstellung reiner Alkali- und/oder Ammonium-Wolframat-Lösungen |
CN104263974A (zh) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | 由钨矿物原料零废水排放制备apt的方法 |
CN104263923A (zh) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | 可实现零污染排放的钨矿物原料冶金工艺 |
CN104263972A (zh) * | 2014-10-09 | 2015-01-07 | 中南大学 | 具有多个闭循环的钨矿物原料冶金系统 |
CN104263975A (zh) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | 具有多个闭循环的钨矿物原料冶金工艺 |
CN104263976A (zh) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | 全程无污染排放的钨矿物原料冶金工艺 |
CN104263973A (zh) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | 由钨矿物原料多闭循环制备apt的方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1377980A (zh) * | 2002-02-06 | 2002-11-06 | 王旭升 | 一种用高钼钨矿制备高纯仲钨酸铵的方法 |
CN101607739A (zh) * | 2008-11-20 | 2009-12-23 | 厦门钨业股份有限公司 | 仲钨酸铵结晶母液闭路循环工艺 |
CN102296179B (zh) * | 2011-08-31 | 2014-11-26 | 鹤山市沃得钨钼实业有限公司 | 钨钼共生混合矿加工生产钨钼产品的方法 |
CN103103359B (zh) * | 2012-11-23 | 2014-05-14 | 陈泉兴 | 一种利用apt废低度钨渣再生apt的方法 |
CN103266231B (zh) * | 2013-05-23 | 2015-08-05 | 中南大学 | 一种高效清洁的钨冶炼方法 |
-
2014
- 2014-10-09 CN CN201410528924.9A patent/CN104263976B/zh not_active Expired - Fee Related
-
2015
- 2015-08-21 WO PCT/CN2015/087823 patent/WO2016054952A1/zh active Application Filing
- 2015-08-21 EP EP15848554.0A patent/EP3205733A1/en not_active Withdrawn
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19724183A1 (de) * | 1996-07-05 | 1998-01-08 | Starck H C Gmbh Co Kg | Verfahren zur Herstellung reiner Alkali- und/oder Ammonium-Wolframat-Lösungen |
CN104263974A (zh) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | 由钨矿物原料零废水排放制备apt的方法 |
CN104263923A (zh) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | 可实现零污染排放的钨矿物原料冶金工艺 |
CN104263972A (zh) * | 2014-10-09 | 2015-01-07 | 中南大学 | 具有多个闭循环的钨矿物原料冶金系统 |
CN104263975A (zh) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | 具有多个闭循环的钨矿物原料冶金工艺 |
CN104263976A (zh) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | 全程无污染排放的钨矿物原料冶金工艺 |
CN104263973A (zh) * | 2014-10-09 | 2015-01-07 | 江西稀有金属钨业控股集团有限公司 | 由钨矿物原料多闭循环制备apt的方法 |
Non-Patent Citations (2)
Title |
---|
WAN, LINSHENG ET AL.: "REACTION PROCESS AND MECHANISM OF SCHEELITE SYNTHESIS WITH WOLFRAMITE AND CALCIUM CARBONATE", RARE METALS AND CEMENTED CARBIDES, vol. 42, no. 2, 30 April 2014 (2014-04-30), XP009501714 * |
WAN, LINSHENG ET AL.: "RESEARCH DIRECTION AND TECHNICAL PROGRESS OF GREEN TUNGSTEN METALLURGY", NONFERROUS METALS SCIENCE AND ENGINEERING, vol. 4, no. 5, 31 October 2013 (2013-10-31), pages 18, XP009501730 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113106248A (zh) * | 2021-03-01 | 2021-07-13 | 崇义章源钨业股份有限公司 | 钨矿物转型预处理方法 |
CN113106248B (zh) * | 2021-03-01 | 2022-09-30 | 崇义章源钨业股份有限公司 | 钨矿物转型预处理方法 |
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