CN115029565B - Preparation method of high-solubility molybdenum baked sand - Google Patents
Preparation method of high-solubility molybdenum baked sand Download PDFInfo
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- CN115029565B CN115029565B CN202210520314.9A CN202210520314A CN115029565B CN 115029565 B CN115029565 B CN 115029565B CN 202210520314 A CN202210520314 A CN 202210520314A CN 115029565 B CN115029565 B CN 115029565B
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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
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum from spent catalysts
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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
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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
- C22B34/34—Obtaining molybdenum
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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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
Abstract
The invention discloses a preparation method of high-solubility molybdenum calcine, which comprises the steps of uniformly mixing a molybdenum-containing raw material with a phosphorus-containing auxiliary agent, and roasting at 600-750 ℃ to obtain molybdenum calcine. The method utilizes the phosphorus-containing auxiliary agent to promote the high-temperature decomposition and conversion of the molybdenum-containing raw material into the molybdenum calcine with high ammonia solubility, more than 95 percent of molybdenum in the molybdenum calcine can be leached and dissolved in ammonia water under normal pressure, is a high-quality raw material for preparing ammonium molybdate, has simple and efficient operation and low raw material cost, has wide adaptability to the molybdenum-containing raw material, and is beneficial to large-scale production.
Description
Technical Field
The invention relates to a preparation method of molybdenum baked sand, in particular to a method for converting molybdenum in a molybdenum-containing raw material into high ammonia-soluble molybdenum trioxide by utilizing a phosphorus-containing auxiliary agent to promote high-temperature decomposition and impurity fixation of the molybdenum-containing raw material, belonging to the technical field of molybdenum metallurgy.
Background
Ammonium molybdate is one of the main industrial products of molybdenum extraction metallurgy and is widely used for producing high-purity molybdenum trioxide, molybdenum products, molybdenum catalysts, molybdenum pigments and the like. At present, more than 95% of ammonium molybdate in the market is obtained by processing molybdenum concentrate, and the rest is extracted and prepared from secondary resources such as waste catalyst, alloy waste, smelting slag and the like.
The oxidative roasting-ammonia leaching process is the dominant method for industrially producing ammonium molybdate. In the oxidizing roasting process, the molybdenum concentrate is heated to 550-700 ℃, and roasted for 5-8 hours in a hot air stream, and molybdenite is converted into molybdenum trioxide and remains in the calcine. The calcine is leached with ammonia water, and the molybdenum can be separated into solution. Purifying, concentrating and acid precipitating the leaching solution to obtain pure ammonium molybdate. The main flow process has the advantages of mature technology, simple equipment, large treatment capacity and the like, and has the obvious defects that: the roasting process is carried out by MoO 3 The molybdates such as calcium, iron (II), magnesium, lead and the like generated by combining with various impurities are difficult to dissolve in ammonia water, so that the recovery rate of molybdenum in the ammonia leaching process is low.
Aiming at the problem of poor ammonia solubility of molybdenum in calcine, the existing solution is to add a hydrochloric acid/nitric acid pickling process before ammonia leaching, and remove impurities in molybdenum calcine by utilizing the reaction of strong acid and molybdate. The acid washing method improves the solubility of molybdenum in the calcine to a certain extent, but the addition of the acid washing procedure inevitably leads to the reduction of production efficiency and the increase of production cost. In addition, the components of the molybdenum calcine pickling waste liquid are complex, so that the national requirements on wastewater discharge are difficult to reach even though the molybdenum calcine pickling waste liquid is treated. Therefore, the industry is advocating the use of water washing instead of acid washing to remove impurities from molybdenum calcine. However, a large amount of poorly soluble molybdate impurities cannot be removed by water washing, so the water washing method is limited to the treatment of high quality molybdenum raw materials.
In summary, the existing mainstream oxidative roasting-acid washing-ammonia leaching process for preparing ammonium molybdate faces huge environmental protection pressure, while the environment-friendly oxidative roasting-water washing-ammonia leaching process for preparing ammonium molybdate cannot adapt to molybdenum raw materials with more impurities due to poor ammonia solubility of calcine.
Disclosure of Invention
Aiming at the problem of poor ammonia solubility of molybdenum calcine produced by an oxidation roasting method in the prior art, the invention aims to provide a preparation method of high-solubility molybdenum calcine, which utilizes a phosphorus-containing auxiliary agent to promote high-temperature decomposition of molybdenum-containing raw materials and realize effective fixation of metal impurities therein, thereby promoting decomposition and conversion of molybdate phase into MoO which is easy to be leached by ammonia water 3 The method is simple to operate, high in efficiency, low in cost and beneficial to large-scale production. The method is simple to operate, high in efficiency, low in cost and beneficial to large-scale production.
In order to achieve the technical aim, the invention provides a preparation method of high-solubility molybdenum calcine, which comprises the steps of uniformly mixing a molybdenum-containing raw material with a phosphorus-containing auxiliary agent, and roasting at 600-750 ℃ to obtain the molybdenum calcine.
The key point of the invention is that the phosphorus-containing auxiliary agent is adopted to carry out high-temperature roasting with the molybdenum-containing raw material, and the phosphorus-containing auxiliary agent can not only promote the high-temperature pyrolysis of the molybdenum-containing raw material at a proper roasting temperature, but also can strongly combine impurity metals in the molybdenum-containing raw material to form metal phosphate, and molybdenum is efficiently converted into molybdenum trioxide to be present in molybdenum calcine, so that the molybdenum calcine can leach metal molybdenum through ammonia water.
As a preferred scheme, the molybdenum-containing raw material comprises at least one of molybdenum concentrate, molybdenum-containing dead catalyst, molybdenum-containing alloy scrap, molybdenum ammonia leaching residue and molybdenum volatile residue. Molybdenum concentrates are commonly known as molybdenite concentrates, iron molybdenite concentrates, calcium molybdate concentrates, and the like. These molybdenum-containing feedstocks are molybdenum-containing feedstocks having a relatively low molybdenum grade, typically less than 60%. The grade of molybdenum concentrate is generally between 30 and 60 percent, and the grade of molybdenum ammonia leaching slag, molybdenum volatile slag and the like is generally lower than 30 percent. These molybdenum-containing feedstocks are suitable for use in the process of the invention.
As a preferred scheme, the phosphorus-containing auxiliary agent comprises at least one of aluminum metaphosphate, aluminum dihydrogen phosphate, aluminum tripolyphosphate, calcium metaphosphate, calcium dihydrogen phosphate, silicon pyrophosphate and ferric pyrophosphate. Or the phosphorus-containing auxiliary agent is converted into at least one of aluminum orthophosphate, calcium pyrophosphate, silicon orthophosphate and ferric orthophosphate under the high temperature effect. These phosphorous-containing adjuvants are used to decompose molybdates at high temperatures and undergo solid-solid reactions with impurities to convert the impurities to phosphates, thereby avoiding molybdate formation. Preferably, phosphorous auxiliaries with dehydration and pore-forming functions such as aluminum dihydrogen phosphate, calcium dihydrogen phosphate and the like are adopted, so that the subsequent high-temperature reaction process can be enhanced, and the internal diffusion condition of the oxidation stage can be improved. Taking the high temperature solid phase reaction of calcium molybdate concentrate and aluminum orthophosphate as an example, the main reaction is as follows: 2CaMoO 4 +Al(PO 3 ) 3 ＝Ca 2 P 2 O 7 +2MoO 3 +AlPO 4 Aluminum metaphosphate can promote the decomposition and conversion of calcium molybdate minerals into calcium pyrophosphate and molybdenum trioxide, and phosphate realizes the fixation of calcium.
As a preferable scheme, the mass of the phosphorus-containing auxiliary agent is 3-30% of the mass of the molybdenum-containing raw material. Generally, the phosphorus-containing auxiliary agent is selected and added according to the content of impurity metal in the molybdenum-containing raw material, the higher the grade of the molybdenum-containing raw material is, the smaller the grade of the molybdenum-containing raw material is, the higher the content of the impurity metal is, and the higher the additive amount is possibly required.
As a preferred scheme, the molybdenum-containing raw material and the phosphate activator are mixed in the form of powder and then baked, or the molybdenum-containing raw material and the phosphate activator are mixed in the form of powder and then pressed into a block or formed into granules, and then baked. The mass percentage content of the powder with the granularity smaller than 200 meshes in the powder is more than 90 percent; the mass percentage content of the granules or the agglomerate materials with the granularity larger than 3mm accounts for more than 75 percent. The mixing process is realized by a ball mill, a powerful mixer, a wet mill or a cylindrical mixer. When molybdenum in the molybdenum-containing raw material mainly exists in the form of low-valence molybdenum such as molybdenite, molybdenum dioxide or metallic molybdenum, the block materials can be prepared and then baked, and the characteristic of developed pores among the block materials is utilized, so that the subsequent high-temperature oxidation mass transfer is facilitated. Or mixing by a cylindrical mixer or ball milling by a ball mill, and then mixing by the cylindrical mixer, wherein the cylindrical mixer can realize pelletization while mixing materials to obtain pellets. When the raw materials are molybdenum calcine/industrial molybdenum oxide, molybdenum-containing dead catalyst and molybdenum ammonia leaching residue, the powder can be directly prepared by adopting a ball mill, a powerful mixer or a wet mill. In preparing the briquettes or pellets, the phosphate activator may be mixed with the molybdenum feedstock in the form of a solution or slurry and then granulated. In the preparation of the powder, the phosphate activator is preferably mixed with the molybdenum raw material in the form of a solid mass. As a preferable scheme, a suitable roasting reactor for the agglomerate is a moving bed such as a rotary kiln, a multi-hearth furnace and the like.
As a preferable scheme, the roasting time is 0.5-3 h. The roasting temperature in the roasting process is an important condition for controlling the phase transformation of the molybdenum-containing raw material, and when the roasting temperature is lower than 600 ℃, the phosphorus-containing auxiliary agent can react with calcium molybdate and molybdenum trioxide to generate a stable calcium phosphomolybdate phase: caMoO 4 +Al(PO 3 ) 3 +21MoO 3 ＝Ca 3 (PMo 12 O 40 ) 2 +AlPO 4 Resulting in molybdenum still being difficult to leach with ammonia; when the roasting temperature is higher than 750 ℃, molybdenum trioxide can be volatilized obviously, a great amount of molybdenum is lost into smoke dust, so that the retention rate of molybdenum in the roasted product is reduced, and the roasting time has less obvious influence on the phase transformation of the molybdenum-containing raw material than the roasting temperature.
As a preferable scheme, the roasting atmosphere is selected according to actual needs, if the molybdenum-containing raw material contains low-valence molybdenum or molybdenum sulfide and the like, an oxygen-containing atmosphere is generally adopted to facilitate the conversion of molybdenum into high-valence molybdenum, and the preferable oxygen-containing atmosphere is at least one of air, oxygen-enriched air, circulating flue gas, fuel gas/fire coal/fuel hot air.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the invention utilizes the phosphorus-containing auxiliary agent to promote the high-temperature conversion of the molybdenum-containing raw material, molybdenum in the formed molybdenum calcine mainly exists in the form of molybdenum trioxide, and impurities mostly exist in the form of phosphate, more than 95% of molybdenum in the molybdenum calcine can be dissolved in ammonia water through normal pressure leaching, and the molybdenum calcine is a high-quality raw material for preparing ammonium molybdate.
The method has the advantages of simple and efficient operation, low raw material cost, wide adaptability to the molybdenum-containing raw material and contribution to large-scale production.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further illustrated and described below in connection with examples, the scope of the claims of the invention being not limited by the following examples.
Example 1
Adding 7.2% of aluminum dihydrogen phosphate into 49.5% grade molybdenite concentrate, uniformly mixing and granulating by a cylinder mixer to obtain lump materials (the material ratio of 3-8 mm is more than 80%), and then placing the lump materials into a rotary tube furnace to be roasted for 2 hours at 650 ℃ in an air atmosphere to obtain molybdenum calcine. After grinding molybdenum calcine, adding ammonia water according to a liquid-solid mass ratio of 3:1, regulating and controlling the pH value of slurry to 8.5, stirring and leaching at 75 ℃ for 60min, and then taking leaching residue for testing, so that the dissolution rate of molybdenum in the calcine is calculated to be as high as 98.4%.
Example 2
The difference from example 1 is that: the addition amount of the calcium dihydrogen phosphate is up to 10.6%, the calcium dihydrogen phosphate is roasted for 2 hours at 700 ℃, and the leaching rate of ammonia after roasting is up to more than 98%.
Example 3
Adding 14.5% of aluminum dihydrogen phosphate into 39.1% grade molybdenite concentrate, uniformly mixing and granulating by a cylinder mixer to obtain lump materials (the material ratio of 3-8 mm is more than 85%), then loading into a rotary tube furnace, and sequentially roasting at 550 ℃ and 650 ℃ for 1h (the roasting atmosphere is air atmosphere) to obtain molybdenum calcine. After grinding molybdenum calcine, adding ammonia water according to a liquid-solid mass ratio of 3:1, regulating and controlling the pH value of slurry to 8.5, stirring and leaching at 75 ℃ for 60min, and then taking leaching residue for testing, so that the dissolution rate of molybdenum in the calcine is calculated to be as high as 97.4%.
Example 4
Adding 25% silicon pyrophosphate into ammonia leaching residue with molybdenum content of 22.7%, ball milling and mixing to obtain powder (-200 mesh 90%), feeding into muffle furnace, and roasting at 650deg.C for 2 hr to obtain molybdenum calcine. Adding ammonia water into the molybdenum calcine according to the liquid-solid mass ratio of 3:1, regulating and controlling the pH value of slurry to 8.5, stirring and leaching at 75 ℃ for 60min, and then leaching residues for assay, so that the dissolution rate of molybdenum in the calcine is calculated to be as high as 95.6%.
Comparative example 1
The same raw materials and operating conditions as in example 3 and example 4 were employed without the addition of phosphorus-containing adjuvants, with only 75.4% and 21.6% respectively of molybdenum dissolution rate in the ammonia leaching process. Because most of molybdate is decomposed by high Wen Nan, molybdenum calcine obtained by directly roasting low-grade molybdenum raw materials has poor ammonia solubility.
Comparative example 2
Unlike example 3: the material with the particle size less than 3mm accounts for 40% of the prepared agglomerate, the agglomerate is put into a rotary tube and is baked for 1 hour at 550 ℃ and 650 ℃ to obtain molybdenum calcine. Then taking calcine ammonia leaching, and reducing the molybdenum leaching rate to 88.7%. When the proportion of fine particles in the lump materials is high, the fluidity of the materials in the rotary pipe is poor, and part of the materials are not fully contacted with air, so that the oxidation effect of the materials is general, and the ammonia solubility of molybdenum calcine is poor.
Comparative example 3
The difference from example 4 is that: roasting for 5 hours at 480 ℃, and then taking calcine ammonia leaching, wherein the molybdenum leaching rate is only 33.6%. The results indicate that the phosphorous-containing adjuvant is not effective at decomposing the molybdate in the ammonia leaching residue at the lower firing temperatures.
Claims (5)
1. A preparation method of high-solubility molybdenum baked sand is characterized by comprising the following steps: uniformly mixing a molybdenum-containing raw material with a phosphorus-containing auxiliary agent, and roasting at 600-750 ℃ under an oxygen-containing atmosphere to obtain molybdenum calcine;
the phosphorus-containing auxiliary agent comprises at least one of aluminum metaphosphate, aluminum dihydrogen phosphate, aluminum tripolyphosphate, calcium metaphosphate, calcium dihydrogen phosphate, silicon pyrophosphate and ferric pyrophosphate;
the molybdenum-containing raw material comprises at least one of molybdenum concentrate, molybdenum-containing dead catalyst, molybdenum-containing alloy waste, molybdenum ammonia leaching slag and molybdenum volatile slag.
2. The method for preparing the high-solubility molybdenum baked sand according to claim 1, which is characterized in that: the mass of the phosphorus-containing auxiliary agent is 3-30% of the mass of the molybdenum-containing raw material.
3. The method for preparing the high-solubility molybdenum baked sand according to claim 1, which is characterized in that: the molybdenum-containing raw material and the phosphorus-containing auxiliary agent are mixed in a powder form and then are roasted, or the molybdenum-containing raw material and the phosphorus-containing auxiliary agent are mixed in a powder form and then are pressed into agglomerate blocks or are made into granules, and then are roasted.
4. A method for preparing high-solubility molybdenum baked sand according to claim 3, characterized in that:
the mass percentage content of the powder with the granularity smaller than 200 meshes in the powder is more than 90 percent;
the mass percentage content of the granules or the agglomerate materials with the granularity larger than 3mm accounts for more than 75 percent.
5. The method for preparing the high-solubility molybdenum baked sand according to claim 1, which is characterized in that: the roasting time is 0.5-3 h.
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Citations (7)
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| US4273745A (en) * | 1979-10-03 | 1981-06-16 | Amax Inc. | Production of molybdenum oxide from ammonium molybdate solutions |
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| CN108913916A (en) * | 2018-07-27 | 2018-11-30 | 成都虹波钼业有限责任公司 | A kind of method of molybdenum in normal pressure leaching calcium molybdate |
| CN110527847A (en) * | 2019-09-17 | 2019-12-03 | 南华大学 | A method of dynamax is obtained by nickel-molybdenum ore |
| CN111926175A (en) * | 2019-05-16 | 2020-11-13 | 中南大学 | Method for extracting molybdenum trioxide by using molybdenum concentrate sulfur dioxide to assist calcification roasting |
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2022
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| US4273745A (en) * | 1979-10-03 | 1981-06-16 | Amax Inc. | Production of molybdenum oxide from ammonium molybdate solutions |
| US4721606A (en) * | 1982-08-20 | 1988-01-26 | Union Oil Company Of California | Recovery of metal values from spent catalysts |
| CN101705364A (en) * | 2009-11-19 | 2010-05-12 | 灵宝市金源矿业有限责任公司 | Comprehensive recycling technology of high-charcoal molybdenum-containing gold and silver ore |
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| CN108913916A (en) * | 2018-07-27 | 2018-11-30 | 成都虹波钼业有限责任公司 | A kind of method of molybdenum in normal pressure leaching calcium molybdate |
| CN111926175A (en) * | 2019-05-16 | 2020-11-13 | 中南大学 | Method for extracting molybdenum trioxide by using molybdenum concentrate sulfur dioxide to assist calcification roasting |
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