CN106222406A - A kind of sulfuric acid system tantalum niobium concentrate pressurization decomposition method - Google Patents

A kind of sulfuric acid system tantalum niobium concentrate pressurization decomposition method Download PDF

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Publication number
CN106222406A
CN106222406A CN201610681286.3A CN201610681286A CN106222406A CN 106222406 A CN106222406 A CN 106222406A CN 201610681286 A CN201610681286 A CN 201610681286A CN 106222406 A CN106222406 A CN 106222406A
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China
Prior art keywords
tantalum
pressure leaching
niobium
pressure
sulfate
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CN201610681286.3A
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Chinese (zh)
Inventor
杨秀丽
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江西理工大学
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Priority to CN201610681286.3A priority Critical patent/CN106222406A/en
Publication of CN106222406A publication Critical patent/CN106222406A/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08Sulfuric acid, other sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10Hydrochloric acid, other halogenated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/20Obtaining niobium, tantalum or vanadium
    • C22B34/24Obtaining niobium or tantalum
    • Y02P10/234

Abstract

The invention discloses a kind of sulfuric acid system tantalum niobium concentrate pressurization decomposition method, initially with mass concentration be 15~30% hydrochloric acid as pressure leaching agent will contain under normal temperature and pressure conditions tantalum niobium concentrate thing with other decompose minerals separation, the pressure leaching time is 0.5~3 hour, after filtering, filtering residue uses concentrated sulphuric acid and sulfate mixture pressure leaching under an increased pressure, filtering residue: concentrated sulphuric acid: the mass ratio of sulfate is 1:0.6~2:0.6~1.2, pressure leaching temperature is 100~350 DEG C, the pressure leaching time is 1~3h, pressure is 0.2~1.2MPa, pressure leaching ore pulp is through filtering, after pickling, the pressure leaching rate of tantalum reaches more than 90%, the pressure leaching rate of niobium reaches more than 95%.

Description

A kind of sulfuric acid system tantalum niobium concentrate pressurization decomposition method

Technical field

The invention belongs to tantalum niobium concentrate material technology field, particularly relate to a kind of sulfuric acid system tantalum niobium concentrate pressurization decomposition method.

Background technology

Tantalum, niobium belong to rare precious metal.Tantalum has the excellent spies such as hardness is big, dielectric constant is big, resistivity is high, corrosion-resistant Property, mainly for the production of capacitor (accounting for more than the 60% of tantalum aggregate consumption).Niobium is then classic steel microalloy element, by with The niobium making steel alloy additive accounts for more than the 90% of niobium aggregate consumption.In recent years, developing rapidly along with electronics and information industry With the sustainable growth of high added value steel products demand, promote China tantalum niobium industry to develop rapidly, thus be tantalum niobium hydrometallurgy Development create excellent opportunity.

At present, domestic and international Tan Ni enterprise all uses highly concentrated Fluohydric acid. (60-70%) or highly concentrated Fluohydric acid .-concentrated sulphuric acid mixing Acid decomposes tantalum niobium concentrate stone at 90-110 DEG C.Under such extreme condition, except rare earth, alkaline earth element generate slightly solubility fluoride or Sulfate remains in slag China and foreign countries, and tantalum, niobium and impurity iron, tungsten, manganese, titanium, silicon etc. all enter solution with fluoro complex form.Tantalum per ton Niobium ore about consumes Fluohydric acid. 4 tons, if decomposing more low-grade tantalum niobium concentrate stone acid consumption, reaches 6-8 ton.Residual hydrogen after decomposition Fluoric acid enters in waste liquid, and waste liquid produces 10-15 ton residue Han fluorite after quick lime neutralisation treatment.Owing to Fluohydric acid. is volatile, In acid hemolysis process, about 10% Fluohydric acid. volatilizees with the form of waste gas containing fluoride, and the generation of substantial amounts of fluorine-containing waste residue and waste gas is to ecology Environment causes severe contamination.

In recent years, the Heavy environmental pollution caused for Fluohydric acid. technique, subsidiary of Bayer Bitterfeld GmbH group is by improving The internal hydrogen fluoric acid medium circulation approach of tantalum niobium hydrometallurgical processes, and strictly control medium consumption, reduce the chemical principle such as HF The consumption of material, and use Free HF in vacuum evaporation Recycling of waste liquid material, fluorine-containing waste residue produced by end will be produced simultaneously It is used for producing calcium sulfate, calcium fluoride or as other chemical raw material, puts into and the generation of slag reducing raw material.China Zhuzhou is hard After matter alloy cluster company limited uses first condensation, the method for drip washing reclaims HF, and the response rate about reaches 70%.Han Jianshe etc. propose Graphite condensed absorbent HF technique, the HF response rate is up to 50%-80%, and recovering effect is preferable.But above method broadly falls into HF end End is administered, and cost is relatively big, and effect is the most thorough, it is impossible to fundamentally solve a fluoride pollution difficult problem.

It addition, being continuously increased recently as tantalum niobium product consumption, high-grade tantalum niobium hard-rock mine is the most far from The market demand can be met.Although China's explored tantalum niobium resource relatively horn of plenty, reserves are at the forefront in the world, but major part tantalum niobium concentrate Grade is the lowest, other mineral of normal association, and disseminated grain size is thin, belongs to complicated difficult mineral.Existing Fluohydric acid. traditional handicraft To the resolution ratio of difficult tantalum niobium resource less than 85%, resource utilization is low, causes the most serious tantalum niobium wasting of resources.

As it has been described above, existing Fluohydric acid. process environments is seriously polluted and resource utilization is low, these problems are the most seriously made The about sustainable development of China tantalum niobium metallurgical industry.The green metallurgical new technique of research and development tantalum niobium resources sustainable development, Alleviate environmental pollution, improve resource utilization, it is achieved tantalum, the clean and effective of niobium extract the crucial section having become in the urgent need to address Skill problem.

Summary of the invention

It is an object of the invention to provide a kind of sulfuric acid system tantalum niobium concentrate pressurization decomposition method, it is intended to solve background technology and carry The problem gone out.

A kind of sulfuric acid system tantalum niobium concentrate pressurization decomposition method, this sulfuric acid system tantalum niobium concentrate pressurization decomposition method, including following Step:

Step one, tantalum-niobium concentrate being milled to 0.038mm~0.106mm, being subsequently placed in mass concentration is 15%~30% In hydrochloric acid, pressure leaching 0.5h~3h at normal temperatures, the ore pulp obtained after acidleach is through filtering and after washing, obtaining filtering residue;

Step 2, the filtering residue in step one is added in the compound of concentrated sulphuric acid and sulfate, filtering residue in mass ratio: dense sulfur Acid: sulfate=1:0.6~2:0.6~1.2 carries out dispensing;

Step 3, it is 0.2~1.2MPa by compound in step 2 at pressure, under conditions of temperature is 100 DEG C~350 DEG C Pressure leaching 1h~3h, the ore pulp after pressure leaching, after filtering, obtains the filtrate containing tantalum and niobium.

Further, the sulfate in described step 2 be sodium sulfate, potassium sulfate, ammonium sulfate, sodium bisulfate, potassium acid sulfate and One or more in ammonium hydrogen sulfate.

Pressure leaching ore pulp of the present invention has eliminated fluoride pollution from source through filtering direct good effect, improves low The direct recovery rate of grade complexity tantalum niobium concentrate, after washing, the pressure leaching rate of tantalum reaches more than 90%, the pressure leaching rate of niobium reaches More than 95%;

Present invention achieves the efficient pressure leaching of tantalum niobium concentrate, especially Low-grade Refractory Tantalum-Niobium Ore, be greatly enhanced Tantalum niobium resource utilization, technological process is simple;

The present invention solves that existing Fluohydric acid. process environments is seriously polluted and resource utilization is low, seriously constrains China The problem of the sustainable development of tantalum niobium metallurgical industry.Provide a kind of new skill of green metallurgical developing tantalum niobium resources sustainable development Art, alleviates environmental pollution, improves resource utilization.

Accompanying drawing explanation

Fig. 1 is the sulfuric acid system tantalum niobium concentrate pressurization decomposition method flow chart that the embodiment of the present invention provides.

Detailed description of the invention

In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, to the present invention It is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to Limit the present invention.

Below in conjunction with the accompanying drawings and the application principle of the present invention is further described by specific embodiment.

One sulfuric acid system tantalum niobium concentrate of the present invention pressurization decomposition method,

As shown in Figure 1: a kind of sulfuric acid system tantalum niobium concentrate pressurization decomposition method, this sulfuric acid system tantalum niobium concentrate pressurization decomposition side Method, comprises the following steps:

S101: tantalum-niobium concentrate is milled to 0.038mm~0.106mm, being subsequently placed in mass concentration is 15%~30% salt In acid, pressure leaching 0.5h~3h at normal temperatures, the ore pulp obtained after acidleach is through filtering and after washing, obtaining filtering residue;

S102: the filtering residue in S101 is added in the concentrated sulphuric acid compound with sulfate, filtering residue in mass ratio: concentrated sulphuric acid: Sulfate=1:0.6~2:0.6~1.2 carries out dispensing;

S103: be 0.2~1.2MPa at pressure by compound in S102, temperature is pressurizeed under conditions of being 100 DEG C~350 DEG C Leaching 1h~3h, the ore pulp after pressure leaching is through filtering and after washing, obtaining the filtrate containing tantalum and niobium.

Sulfate in described step 2 is sodium sulfate, potassium sulfate, ammonium sulfate, sodium bisulfate, potassium acid sulfate and hydrogen sulfate One or more in ammonium.

Below in conjunction with specific embodiment, the application principle of the present invention is further described.

Embodiment 1

Joining in 200g25% hydrochloric acid by 100g tantalum niobium raw ore, pressure leaching 1h at normal temperatures, after pressure leaching Ore pulp obtains filtering residue through filtration washing.20g filtering residue is put into 40g concentrated sulphuric acid (content 98%) and 24g sodium sulfate carries out dispensing Mixing, puts into autoclave and carries out pressure leaching, and pressure is 1MPa, and temperature is 200 DEG C, and the response time is 1.5h.After pressurized acid leaching Ore pulp through filtration after obtain containing tantalum, the solution of niobium.Through analyzing, tantalum, the pressure leaching rate of niobium respectively reach 90.21% and 95.32%.

Embodiment 2

Joining in 200g35% hydrochloric acid by 100g tantalum niobium raw ore, pressure leaching 0.5h at normal temperatures, after pressure leaching Ore pulp obtain filtering residue through filtration washing.20g filtering residue is put into 30g concentrated sulphuric acid (content 98%) and 20g sodium sulfate is joined Material mixing, puts into autoclave and carries out pressure leaching, and pressure is 1MPa, and temperature is 220 DEG C, and the response time is 1.8h.Pressurized acid leaching After ore pulp through filtration after obtain containing tantalum, the solution of niobium.Through analyzing, tantalum, the pressure leaching rate of niobium respectively reach 90.81% With 95.68%.

Embodiment 3

Joining in 200g20% hydrochloric acid by 100g tantalum niobium raw ore, pressure leaching 0.7h at normal temperatures, after pressure leaching Ore pulp obtain filtering residue through filtration washing.20g filtering residue is put into 20g concentrated sulphuric acid (content 98%) and 24g sodium sulfate is joined Material mixing, puts into autoclave and carries out pressure leaching, and pressure is 1.2MPa, and temperature is 260 DEG C, and the response time is 3h.Pressurized acid leaching After ore pulp through filtration after obtain containing tantalum, the solution of niobium.Through analyzing, tantalum, the pressure leaching rate of niobium respectively reach 90.87% With 95.99%.

Embodiment 4

Joining in 300g15% hydrochloric acid by 100g tantalum niobium raw ore, pressure leaching 1h at normal temperatures, after pressure leaching Ore pulp obtains filtering residue through filtration washing.20g filtering residue is put into 40g concentrated sulphuric acid (content 98%) and 24g ammonium sulphate carries out dispensing Mixing, puts into autoclave and carries out pressure leaching, and pressure is 1MPa, and temperature is 200 DEG C, and the response time is 2.5h.After pressurized acid leaching Ore pulp through filtration after obtain containing tantalum, the solution of niobium.Through analyzing, tantalum, the pressure leaching rate of niobium respectively reach 90.65% and 95.76%.

Embodiment 5

Joining in 300g18% hydrochloric acid by 100g tantalum niobium raw ore, pressure leaching 1h at normal temperatures, after pressure leaching Ore pulp obtains filtering residue through filtration washing.20g filtering residue is put into 26g concentrated sulphuric acid (content 98%) and 24g potassium sulfate carries out dispensing Mixing, puts into autoclave and carries out pressure leaching, and pressure is 1MPa, and temperature is 240 DEG C, and the response time is 2.4h.After pressurized acid leaching Ore pulp through filtration after obtain containing tantalum, the solution of niobium.Through analyzing, tantalum, the pressure leaching rate of niobium respectively reach 90.77% and 95.78%.

Embodiment 6

Joining in 200g22% hydrochloric acid by 100g tantalum niobium raw ore, pressure leaching 1.2h at normal temperatures, after pressure leaching Ore pulp obtain filtering residue through filtration washing.20g filtering residue is put into 30g concentrated sulphuric acid (content 98%) and 24g ammonium sulphate is joined Material mixing, puts into autoclave and carries out pressure leaching, and pressure is 1.2MPa, and temperature is 260 DEG C, and the response time is 2.8h.Pressurization acid Ore pulp after leaching obtains containing tantalum, the solution of niobium after filtering.Through analyzing, tantalum, the pressure leaching rate of niobium respectively reach 90.88% and 95.97%.

Pressure leaching ore pulp of the present invention is through filtering, after pickling, and the pressure leaching rate of tantalum reaches more than 90%, the pressurization of niobium Leaching rate reaches more than 95%;

Present invention achieves the efficient pressure leaching of tantalum niobium concentrate, especially Low-grade Refractory Tantalum-Niobium Ore, be greatly enhanced Tantalum niobium resource utilization, and from source, eliminate fluoride pollution, technological process is simple.

The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.

Claims (2)

1. a sulfuric acid system tantalum niobium concentrate pressurization decomposition method, it is characterised in that this sulfuric acid system tantalum niobium concentrate pressurization decomposition method, Comprise the following steps:
Step one, tantalum-niobium concentrate being milled to 0.038mm~0.106mm, being subsequently placed in mass concentration is 15%~30% hydrochloric acid In, pressure leaching 0.5h~3h at normal temperatures, the ore pulp obtained after acidleach is through filtering and after washing, obtaining filtering residue;
Step 2, the filtering residue in step one is added in the compound of concentrated sulphuric acid and sulfate, filtering residue in mass ratio: concentrated sulphuric acid: Sulfate=1:0.6~2:0.6~1.2 carries out dispensing;
Step 3, it is 0.2MPa~1.2MPa by compound in step 2 at pressure, under conditions of temperature is 100 DEG C~350 DEG C Pressure leaching 1h~3h, the ore pulp after pressure leaching, after filtering, obtains the filtrate containing tantalum and niobium.
2. sulfuric acid system tantalum niobium concentrate pressurization decomposition method as claimed in claim 1, it is characterised in that the sulfur in described step 2 Hydrochlorate is one or more in sodium sulfate, potassium sulfate, ammonium sulfate, sodium bisulfate, potassium acid sulfate and ammonium hydrogen sulfate.
CN201610681286.3A 2016-08-17 2016-08-17 A kind of sulfuric acid system tantalum niobium concentrate pressurization decomposition method CN106222406A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101440429A (en) * 2008-12-18 2009-05-27 广州有色金属研究院 Method for decomposing ore concentrate containing tantalum, niobium and rare-earth element
CN101492771A (en) * 2009-03-04 2009-07-29 广州有色金属研究院 Hingganite ore concentrate decomposition method
CN102703682A (en) * 2012-06-29 2012-10-03 广州有色金属研究院 Comprehensive recovery method of rare metal ore
CN103415631A (en) * 2011-01-06 2013-11-27 阿海珐矿业公司 Dissolution and recovery of at least one element nb or ta and of at least one other element u or rare earth elements from ores and concentrates
CN104745807A (en) * 2013-12-31 2015-07-01 北京有色金属研究总院 Method for extracting valuable metal elements in niobium-tantalum ore
CN105331811A (en) * 2014-08-06 2016-02-17 北京有色金属研究总院 Method for extracting tantalum, niobium and rare earth elements in multi-metal associated tantalum-niobium ores

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101440429A (en) * 2008-12-18 2009-05-27 广州有色金属研究院 Method for decomposing ore concentrate containing tantalum, niobium and rare-earth element
CN101492771A (en) * 2009-03-04 2009-07-29 广州有色金属研究院 Hingganite ore concentrate decomposition method
CN103415631A (en) * 2011-01-06 2013-11-27 阿海珐矿业公司 Dissolution and recovery of at least one element nb or ta and of at least one other element u or rare earth elements from ores and concentrates
CN102703682A (en) * 2012-06-29 2012-10-03 广州有色金属研究院 Comprehensive recovery method of rare metal ore
CN104745807A (en) * 2013-12-31 2015-07-01 北京有色金属研究总院 Method for extracting valuable metal elements in niobium-tantalum ore
CN105331811A (en) * 2014-08-06 2016-02-17 北京有色金属研究总院 Method for extracting tantalum, niobium and rare earth elements in multi-metal associated tantalum-niobium ores

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
OMNEYA M. EL-HUSSAINI 等: "Sulfuric acid leaching of Kab Amiri niobium-tantalum bearing minerals, Central Eastern Desert,Egypt", 《HRDROMETALLURGY》 *
XIULI YANG 等: "Kinetics of pressure leaching of niobium ore by sulfuric acid", 《INT. JOURNAL OF REFRACTORY METALS AND HARD MATERIALS》 *

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