CN103866142A - Method of recycling molybdenum and rhenium from molybdenum concentrate by hydrometallurgy - Google Patents

Method of recycling molybdenum and rhenium from molybdenum concentrate by hydrometallurgy Download PDF

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CN103866142A
CN103866142A CN201410120102.7A CN201410120102A CN103866142A CN 103866142 A CN103866142 A CN 103866142A CN 201410120102 A CN201410120102 A CN 201410120102A CN 103866142 A CN103866142 A CN 103866142A
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China
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filtrate
molybdenum
step
rhenium
gac
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CN201410120102.7A
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Chinese (zh)
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曹亮
李来平
蒋丽娟
张新
刘燕
李延超
杨健
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西北有色金属研究院
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/234Recovering metals from waste by hydro metallurgy

Abstract

The invention provides a method of recycling molybdenum and rhenium from molybdenum concentrate by hydrometallurgy. The method comprises the following steps: I, mixing molybdenum concentrate powder with deionized water to prepare ore pulp; II, carrying out pressurizing oxidization treatment onto the ore pulp; III, filtering to obtain a filter cake and filtrate; and IV, respectively treating the filter cake and the filtrate: drying the filter cake to obtain industrial molybdenum oxide; carrying out precipitation and impurity removal, active carbon adsorption and solid-liquid separation treatment onto the filtrate in sequence, crystallizing the filtrate treated by solid-liquid separation to obtain ammonium molybdate, and desorbing and crystallizing rhenium on the active carbon treated by the solid-liquid separation to obtain ammonium perrhenate. The method disclosed by the invention is simple in process, strong in repeatability, high in recovery rate of the molybdenum and the rhenium and suitable for large-scale industrial production.

Description

A kind of from concentrated molybdenum ore the method for hydrometallurgical recovery molybdenum and rhenium

Technical field

The invention belongs to technical field of wet metallurgy, be specifically related to a kind of from concentrated molybdenum ore the method for hydrometallurgical recovery molybdenum and rhenium.

Background technology

Since 20 century 70s, in succession develop the full hydrometallurgical processes of many molybdenum glances both at home and abroad, comparative maturity have nitric acid oxidation decomposition technique, Oxidation under pressurized oxygen technique (being called for short POX) and clorox decomposition technique, a present report that also occurs biological oxidation process.Pressure oxidation hydrometallurgy because technical process is short, metal recovery rate is high, the feature such as, environmental friendliness strong to dissimilar adaptability to raw material developed rapidly.Pressure oxidation hydrometallurgical technology, since occurring, has been subject to many internationally famous mining companies giving more sustained attention as the company such as AMAX, KENNECOTT of the U.S..To this technology, carry out large quantity research abroad, having obtained good effect aspect the maturity of technology, equipment and technology controlling and process, have multinomial Patents.

Compared with pressure leaching leaches with normal pressure, with the obvious advantage.Normal pressure leaching process is to carry out under room temperature or the condition below solution boiling temperature mostly, and leaching velocity is often slow, extraction time that need to be longer.Pressure leaching is in airtight reaction vessel, temperature of reaction is brought up to solution boiling point carries out above, and principal feature is to improve extraction temperature, accelerate leaching velocity, thereby greatly shorten extraction time.Pressure leaching is the hydrothermal reaction process that liquid one is solid or gas one liquid one solid phase is carried out under high-temperature pressurizing condition.The reaction that pressure leaching can make some can not carry out at normal temperatures and pressures becomes possibility.Pressurization can make the reagent of for example oxygen of some gas or easy volatile have higher dividing potential drop in the time leaching, and reaction can be carried out under more effective condition, thereby strengthened leaching process, has improved the extraction yield of metal.

In recent years, Pressure hydrometallurgy is showing unarguable superiority aspect environment protection and metal separation.Along with deepening continuously of research, Pressure hydrometallurgy has been obtained breakthrough in many-side.It not only reclaims in processing, the platinum metals of Cu, Ni and Co sulfide, zinc sulfide concentrates extracts the aspects such as zinc and difficult-treating gold mine preoxidation and obtains industrial applications, and aspect the pressure leaching of brightness concentrated molybdenum ore, also obtaining impressive progress.

2008, second-biggest-in-the-world molybdenum production company---Kennecott company of the U.S. is by the overall technique assessment to POX technique (being Oxidation under pressurized oxygen), invest 2.7 hundred million dollars and build a molybdenum pressure oxidation production line of producing 30000 tons of industrial molybdenum oxides (be equivalent to U.S.'s molybdenum output in 2008 1/3) per year, plan build up and go into operation the second quarter in 2010.Haggle in advance the rate of recovery that adopts oxidizing roasting method can significantly improve molybdenum, produce approximately 4 tons of dissipated metal rheniums simultaneously, rhenium is as scarce resource, sought-after in recent years, price steadiness.In addition, this method has reached Environmental Protection in America index, and this index is the barrier that calcining molybdenum ore concentrate is difficult to pass through always.The successful Application of pressure oxidation technique in Rio Tinto Group's concentrated molybdenum ore is processed, will change approximately more than the 70 year history with multiple hearth furnace, rotary kiln manufacture molybdenum oxide, has highlighted the applications well prospect of this technique.

Only have in the world at present several companies from concentrated molybdenum ore, to produce rhenium, as (the Climax of Ke Laima Ces Co.,Ltd of not Lyntech Corporation (US) 10177 South 77th East Avenue Tulsa, Oklahoma 74133 U.S. (Molymet) of Chile, the U.S., present Fei Erpudaonai company), your section of Cooley of company of Cyprus of the U.S., Chile (Coolelco, i.e. Chilean national copper company), this company of Herman of Germany, Sumitomo company and the CANON of Japan.About the technology of extracting rhenium from concentrated molybdenum ore, these companies are in early days in highly confidential state.

The operational path that the companies such as Chile, the U.S., Germany reclaim rhenium from molybdenum glance concentrate is mainly by water-soluble the flue dust of concentrated molybdenum ore solution, then from the aqueous solution, extracts rhenium and separates with molybdenum.The method of extracting rhenium is with ion exchange method or solvent extration, then desorb or back extraction, then the crystallization of rhenium-containing solution evaporation is obtained to rhenium salt.

It is shorter that China produces the history of rhenium, and batch production rhenium starts from before and after 1980 after reform and opening-up.Researchist's wet method of Zhuzhou tungsten group company (former Zhuzhou Hard Alloy Plant), pressure oxidation of molybdenite concentrate extracts rhenium from concentrated molybdenum ore.Oxidation under pressurized oxygen carries out in reactor, and temperature is more than 200 ℃, pressure 3~4MPa.Rhenium extraction yield approximately 60~70%, it is said and now stop production.After 2000, Dexing copper mine adopts solvent extration from the flue dust of calcining molybdenum ore concentrate, to reclaim rhenium, limited amount.

Jinduicheng Molybdenum Industry Corp has also studied from calcining molybdenum ore concentrate flue dust and washing smoke liquid and has reclaimed rhenium, has also studied ion exchange method and solvent extration.Because concentrated molybdenum ore rhenium-containing is 15-20g/t, the extremely low recovery difficult of grade is larger, adopts traditional technology economy uneconomical, still belongs at present conceptual phase, and when industrialization needs time.Another Luo Mu Group Co.,Ltd of large-scale molybdenum manufacturing enterprise, at present in the rhenium-containing situation of investigating each branch office of the said firm concentrated molybdenum ore.Also some carries rhenium report in some institutes of junior college, but few, the checking to be analyzed of many molybdenum ore rhenium-containing situations.

Summary of the invention

Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provide a kind of from concentrated molybdenum ore the method for hydrometallurgical recovery molybdenum and rhenium.The method preparation technology is simple, and repeatable strong, the rate of recovery of molybdenum and rhenium metal is high, is suitable for large-scale industrialization and produces.

For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of from concentrated molybdenum ore the method for hydrometallurgical recovery molybdenum and rhenium, it is characterized in that, the method comprises the following steps:

Step 1, by concentrated molybdenum ore powder and deionized water by solid-to-liquid ratio 1: (8~12) mix, and obtain ore pulp; In described concentrated molybdenum ore powder, the quality percentage composition of molybdenum is not less than 45%, and the quality percentage composition of rhenium is 0.02%~0.04%;

Step 2, under oxygen atmosphere, utilize autoclave to carry out pressure oxidation treatment to ore pulp described in step 1, the temperature of described pressure oxidation treatment is 180 ℃~210 ℃, the time of described pressure oxidation treatment is 1.5h~2h, and in pressure oxidation treatment process, the pressure of oxygen is 0.5MPa~0.7MPa;

Step 3, the ore pulp after pressure oxidation treatment in step 2 is carried out to filtration treatment, obtain filter cake and filtrate;

Step 4, filter cake described in step 3 and filtrate are processed respectively:

The treating processes of described filter cake is: filter cake is carried out to drying treatment, obtain industrial molybdenum oxide after naturally cooling;

The treating processes of described filtrate is:

Step 401, employing Sodium sulfhydrate carry out to remove impurity by means of precipitation processing to filtrate, are 7~8 rear filtering throw outs until make the pH value of filtrate;

Step 402, employing ammoniacal liquor are adjusted to 8.5~9.5 by the pH value of the filtrate after filtering throw out in step 401, then gac are added in the filtrate regulating after pH value and stir, in order to the rhenium element in absorption filtrate; The add-on of described gac is in every liter of filtrate, to add 50g~70g gac;

Step 403, the filtrate that is added with gac in step 402 is carried out to solid-liquid separation processing, then solid-liquid separation filtrate after treatment and gac is processed respectively, be specially:

Filtrate after treatment solid-liquid separation is carried out to crystallization treatment, obtain ammonium molybdate;

By solid-to-liquid ratio 1: it is to soak 1h~3h in the deionized water of 60 ℃~80 ℃ that gac after treatment solid-liquid separation is added temperature by (4~10), the rhenium element solution that makes to be adsorbed on gac is drawn in deionized water, then desorb there is is the deionized water of rhenium element to carry out crystallization treatment, obtain ammonium perrhenate.

Above-mentioned a kind of from concentrated molybdenum ore the method for hydrometallurgical recovery molybdenum and rhenium, it is characterized in that, the mass percent concentration of ammoniacal liquor described in step 402 is 25%~28%.

Above-mentioned a kind of from concentrated molybdenum ore the method for hydrometallurgical recovery molybdenum and rhenium, it is characterized in that, the granularity of gac described in step 402 is-100 orders~+ 200 orders.

Technological improvement of the present invention is: first, concentrated molybdenum ore powder and deionized water are hybridly prepared into ore pulp by the present invention.Then, ore pulp is carried out to pressure oxidation treatment, make the molybdenum element generation oxidizing reaction in concentrated molybdenum ore, most molybdenum proceeds in solid phase with the form of molybdic oxide, and the molybdenum of small portion proceeds in liquid phase with molybdate form; Rhenium element in concentrated molybdenum ore all proceeds in liquid phase with rehenic acid root form; The associated minerals such as iron mineral in concentrated molybdenum ore, copper mineral, lead minerals also proceed in liquid phase with forms such as iron ion, cupric ion, lead ions.After filtration, adopt Sodium sulfhydrate to adjust the pH value of filtrate, and the foreign ions such as copper in filtrate, iron, lead are precipitated, thereby realize the object of effective removal of impurities, the filtrate after to remove impurity by means of precipitation is the solution that only contains molybdate and rehenic acid root.Finally, adopt the method for charcoal absorption to make rhenium and molybdenum obtain effective separation.Gac is more than 95% rhenium in adsorbent solution optionally, and molybdenum rhenium separation factor is greater than 3000, and separating effect is good.And on gac, inevitably adhere to ammonium radical ion, finally, after desorb and crystallization, can obtain high-purity ammonium perrhenate crystal.Concrete reaction equation is:

MoS 2+2H 2O+4.5O 2→MoO 3+2H 2SO 4

2CuFeS 2+8.5O 2+H 2SO 4→2CuSO 4+Fe 2(SO 4) 3+H 2O

4Re+7O 2+2H 2O→4HReO 4

Cu 2++HS -→CuS+H +

2Fe 3++3HS -→Fe 2S 3+3H +

Pb 2++HS -→PbS+H +

The present invention compared with prior art has the following advantages:

1, the present invention adopts the mode of pressure oxidation to be oxidized concentrated molybdenum ore, by controlling strict pressure oxidation condition, make molybdenum major part be oxidized to molybdic oxide and proceed to solid phase, make rhenium metal all be converted into rehenic acid radical ion and proceed to liquid phase, rhenium metal leaching rate can be up to 100%, and makes the copper, iron, the lead and other elements that in concentrated molybdenum ore, contain proceed to liquid phase with ionic species.Solid matter after pressure oxidation of the present invention dry after filtration after for oxidation ratio is more than 99% industrial molybdenum oxide, its molybdic oxide content is high, other impurity component is extremely low.

2, the present invention adds Sodium sulfhydrate in the filtrate after pressure oxidation treatment, makes copper, iron, plumbous plasma in filtrate be converted into sulfide precipitation.In this to remove impurity by means of precipitation process, molybdenum, rhenium metal in filtrate can not be converted into throw out, therefore, the present invention adopts Sodium sulfhydrate to carry out in the process of to remove impurity by means of precipitation, and molybdenum, the free of losses of rhenium metal have guaranteed that the rate of recovery of molybdenum, rhenium metal is high.In addition, the present invention has improved the pH value of filtrate when adopting Sodium sulfhydrate to carry out to remove impurity by means of precipitation, has reduced the front required ammonia volume of pH value of adjusting of ionic adsorption technique.

3, the present invention adopts gac as absorption carrier, the rehenic acid root in solution is carried out to selective adsorption, under the condition that is 8.5~9.5 at pH, use activated carbon granule, optionally more than 95% rehenic acid root in adsorbent solution, molybdenum rhenium separation factor is greater than 3000, and separating effect is good.Therefore, adsorption tail liquid is only containing the solution of molybdate, the ammonium molybdate crystal that evaporative crystallization can high purity.And have the activated carbon granule of rhenium element for absorption, and adopt the method for hot-water soak by the abundant desorb of rehenic acid root being adsorbed, after evaporative crystallization, finally obtain high-purity ammonium perrhenate.Activated carbon granule can reuse, and utilization ratio is high.

4, technical process of the present invention is simple, can realize large-scale commercial production.After adopting the present invention to process, the rate of recovery of rhenium metal can reach more than 95%, and molybdenum oxidation ratio can reach more than 99%, and the molybdenum rate of recovery can reach more than 97%.

5, in technological process of the present invention without pollutant emissions such as sulfurous gas, activated carbon granule can be realized recycling, desorb medicament is clear water, industrial production experiment zero pollutant discharge.

Below in conjunction with embodiment, the present invention is described in further detail.

Accompanying drawing explanation

Fig. 1 is process flow diagram of the present invention.

Embodiment

Embodiment 1

In the pending concentrated molybdenum ore of the present embodiment, the quality percentage composition of molybdenum is 55%, and the quality percentage composition of rhenium is 0.04%.In conjunction with Fig. 1, the present embodiment method of hydrometallurgical recovery molybdenum and rhenium from concentrated molybdenum ore comprises the following steps:

Step 1, concentrated molybdenum ore powder is mixed by solid-to-liquid ratio with deionized water at 1: 10, obtain ore pulp;

Step 2, under oxygen atmosphere, utilize autoclave to carry out pressure oxidation treatment to ore pulp described in step 1, the temperature of described pressure oxidation treatment is 180 ℃, the time of described pressure oxidation treatment is 2h, the pressure of described pressure oxidation treatment is 0.6MPa; After pressure oxidation treatment, concentrated molybdenum ore is mainly oxidized to molybdic oxide and proceeds to solid phase, and part molybdenum exists and proceed to liquid phase with molybdate form.There is and proceed to liquid phase with rehenic acid root form in whole rhenium elements, in concentrated molybdenum ore, the impurity such as the iron mineral of association, copper mineral, lead minerals mainly exists and proceed to liquid phase with iron ion, cupric ion, lead ion form;

Step 3, the ore pulp after pressure oxidation treatment in step 2 is carried out to filtration treatment, obtain filter cake and filtrate; In specific implementation process, can use deionized water repeatedly to rinse filter cake, the molybdate of adsorbing in filter cake and rehenic acid root be cleaned and entered in filtrate;

Step 4, filter cake described in step 3 and filtrate are processed respectively:

The treating processes of described filter cake is: filter cake is carried out to drying treatment, obtain industrial molybdenum oxide after naturally cooling;

The treating processes of described filtrate is:

Step 401, employing Sodium sulfhydrate carry out to remove impurity by means of precipitation processing to filtrate, be 7 until make the pH value of filtrate, Sodium sulfhydrate can make copper, iron, the plumbous plasma precipitation in filtrate complete, then adopt the method for filtering by throw out reject, making the filtrate after to remove impurity by means of precipitation is the solution that only contains molybdate and rehenic acid root;

The ammoniacal liquor that step 402, employing mass percent concentration are 27% is adjusted to 9.5 by the pH value of the filtrate after to remove impurity by means of precipitation in step 401, be that to add pH value be in 9.5 filtrate to-100 orders~+ 200 object gac again by granularity, in order to the rhenium element in absorption filtrate, the add-on of described gac is in every liter of filtrate, to add 50g gac;

Step 403, employing are filtered, method centrifugal or sedimentation is carried out solid-liquid separation processing to the filtrate that is added with gac in step 402, then solid-liquid separation filtrate after treatment and gac are processed respectively:

Filtrate after treatment solid-liquid separation is carried out to crystallization treatment, obtain ammonium molybdate;

By solid-to-liquid ratio 1: 4, gac after treatment solid-liquid separation being added to temperature is to soak 2h in the deionized water of 70 ℃, the rhenium element solution that makes to be adsorbed on gac is drawn to liquid phase, because activated carbon surface can inevitably adhere to a small amount of ammonium radical ion, ammonium radical ion also can proceed in deionized water in immersion process, finally, by crystallization treatment, obtain ammonium perrhenate.

The quality percentage composition 55.26% of molybdenum in industrial molybdenum oxide prepared by the present embodiment, the quality percentage composition 54.76% of the molybdenum wherein existing with molybdic oxide form, known as calculated, the oxidation ratio of molybdenum is more than 99%.

In ammonium molybdate prepared by the present embodiment, the quality percentage composition of molybdenum is 54.8%.Known as calculated, the quality purity of ammonium molybdate prepared by the present embodiment is more than 95%.

In ammonium perrhenate prepared by the present embodiment, the quality percentage composition of rhenium is 69.41%.Known as calculated, the quality purity of ammonium perrhenate prepared by the present embodiment is more than 99%.

Embodiment 2

In the pending concentrated molybdenum ore of the present embodiment, the quality percentage composition of molybdenum is 45%, and the quality percentage composition of rhenium is 0.02%.In conjunction with Fig. 1, the present embodiment method of hydrometallurgical recovery molybdenum and rhenium from concentrated molybdenum ore comprises the following steps:

Step 1, concentrated molybdenum ore powder is mixed by solid-to-liquid ratio with deionized water at 1: 10, obtain ore pulp;

Step 2, under oxygen atmosphere, utilize autoclave to carry out pressure oxidation treatment to ore pulp described in step 1, the temperature of described pressure oxidation treatment is 200 ℃, and the time of described pressure oxidation treatment is 1.5h, and the pressure of described pressure oxidation treatment is 0.7MPa; After pressure oxidation treatment, concentrated molybdenum ore is mainly oxidized to molybdic oxide and proceeds to solid phase, and part molybdenum exists and proceed to liquid phase with molybdate form.There is and proceed to liquid phase with rehenic acid root form in whole rhenium elements, in concentrated molybdenum ore, the impurity such as the iron mineral of association, copper mineral, lead minerals mainly exists and proceed to liquid phase with iron ion, cupric ion, lead ion form;

Step 3, the ore pulp after pressure oxidation treatment in step 2 is carried out to filtration treatment, obtain filter cake and filtrate; In specific implementation process, can use deionized water repeatedly to rinse filter cake, the molybdate of adsorbing in filter cake and rehenic acid root be cleaned and entered in filtrate;

Step 4, filter cake described in step 3 and filtrate are processed respectively:

The treating processes of described filter cake is: filter cake is carried out to drying treatment, obtain industrial molybdenum oxide after naturally cooling;

The treating processes of described filtrate is:

Step 401, employing Sodium sulfhydrate carry out to remove impurity by means of precipitation processing to filtrate, be 8 until make the pH value of filtrate, Sodium sulfhydrate can make copper, iron, the plumbous plasma precipitation in filtrate complete, then adopt the method for filtering by throw out reject, making the filtrate after to remove impurity by means of precipitation is the solution that only contains molybdate and rehenic acid root;

The ammoniacal liquor that step 402, employing mass percent concentration are 25% is adjusted to 8.5 by the pH value of the filtrate after to remove impurity by means of precipitation in step 401, be that to add pH value be in 8.5 filtrate to-100 orders~+ 200 object gac again by granularity, in order to the rhenium element in absorption filtrate, the add-on of described gac is in every liter of filtrate, to add 60g gac;

Step 403, employing are filtered, method centrifugal or sedimentation is carried out solid-liquid separation processing to the filtrate that is added with gac in step 402, then solid-liquid separation filtrate after treatment and gac are processed respectively:

Filtrate after treatment solid-liquid separation is carried out to crystallization treatment, obtain ammonium molybdate;

By solid-to-liquid ratio 1: 8, gac after treatment solid-liquid separation being added to temperature is to soak 2h in the deionized water of 70 ℃, the rhenium element solution that makes to be adsorbed on gac is drawn to liquid phase, because activated carbon surface can inevitably adhere to a small amount of ammonium radical ion, ammonium radical ion also can proceed in deionized water in immersion process, finally, by crystallization treatment, obtain ammonium perrhenate.

The quality percentage composition 55.30% of molybdenum in industrial molybdenum oxide prepared by the present embodiment, the quality percentage composition 54.79% of the molybdenum wherein existing with molybdic oxide form, known as calculated, the oxidation ratio of molybdenum is more than 99%.

In ammonium molybdate prepared by the present embodiment, the quality percentage composition of molybdenum is 54.9%.Known as calculated, the quality purity of ammonium molybdate prepared by the present embodiment is more than 95%.

In ammonium perrhenate prepared by the present embodiment, the quality percentage composition of rhenium is 69.39%.Known as calculated, the quality purity of ammonium perrhenate prepared by the present embodiment is more than 99%.

Embodiment 3

In the pending concentrated molybdenum ore of the present embodiment, the quality percentage composition of molybdenum is 57%, and the quality percentage composition of rhenium is 0.04%.In conjunction with Fig. 1, the present embodiment method of hydrometallurgical recovery molybdenum and rhenium from concentrated molybdenum ore comprises the following steps:

Step 1, concentrated molybdenum ore powder is mixed by solid-to-liquid ratio with deionized water at 1: 12, obtain ore pulp;

Step 2, under oxygen atmosphere, utilize autoclave to carry out pressure oxidation treatment to ore pulp described in step 1, the temperature of described pressure oxidation treatment is 180 ℃, the time of described pressure oxidation treatment is 2h, the pressure of described pressure oxidation treatment is 0.5MPa; After pressure oxidation treatment, concentrated molybdenum ore is mainly oxidized to molybdic oxide and proceeds to solid phase, and part molybdenum exists and proceed to liquid phase with molybdate form.There is and proceed to liquid phase with rehenic acid root form in whole rhenium elements, in concentrated molybdenum ore, the impurity such as the iron mineral of association, copper mineral, lead minerals mainly exists and proceed to liquid phase with iron ion, cupric ion, lead ion form;

Step 3, the ore pulp after pressure oxidation treatment in step 2 is carried out to filtration treatment, obtain filter cake and filtrate; In specific implementation process, can use deionized water repeatedly to rinse filter cake, the molybdate of adsorbing in filter cake and rehenic acid root be cleaned and entered in filtrate;

Step 4, filter cake described in step 3 and filtrate are processed respectively:

The treating processes of described filter cake is: filter cake is carried out to drying treatment, obtain industrial molybdenum oxide after naturally cooling;

The treating processes of described filtrate is:

Step 401, employing Sodium sulfhydrate carry out to remove impurity by means of precipitation processing to filtrate, be 8 until make the pH value of filtrate, Sodium sulfhydrate can make copper, iron, the plumbous plasma precipitation in filtrate complete, then adopt the method for filtering by throw out reject, making the filtrate after to remove impurity by means of precipitation is the solution that only contains molybdate and rehenic acid root;

The ammoniacal liquor that step 402, employing mass percent concentration are 28% is adjusted to 9.5 by the pH value of the filtrate after to remove impurity by means of precipitation in step 401, be that to add pH value be in 9.5 filtrate to-100 orders~+ 200 object gac again by granularity, in order to the rhenium element in absorption filtrate, the add-on of described gac is in every liter of filtrate, to add 70g gac;

Step 403, employing are filtered, method centrifugal or sedimentation is carried out solid-liquid separation processing to the filtrate that is added with gac in step 402, then solid-liquid separation filtrate after treatment and gac are processed respectively:

Filtrate after treatment solid-liquid separation is carried out to crystallization treatment, obtain ammonium molybdate;

By solid-to-liquid ratio 1: 10, gac after treatment solid-liquid separation being added to temperature is to soak 1h in the deionized water of 80 ℃, the rhenium element solution that makes to be adsorbed on gac is drawn to liquid phase, because activated carbon surface can inevitably adhere to a small amount of ammonium radical ion, ammonium radical ion also can proceed in deionized water in immersion process, finally, by crystallization treatment, obtain ammonium perrhenate.

The quality percentage composition 58.58% of molybdenum in industrial molybdenum oxide prepared by the present embodiment, the quality percentage composition 58.07% of the molybdenum wherein existing with molybdic oxide form, known as calculated, the oxidation ratio of molybdenum is more than 99%.

In ammonium molybdate prepared by the present embodiment, the quality percentage composition of molybdenum is 54.8%.Known as calculated, the quality purity of ammonium molybdate prepared by the present embodiment is more than 95%.

In ammonium perrhenate prepared by the present embodiment, the quality percentage composition of rhenium is 69.41%.Known as calculated, the quality purity of ammonium perrhenate prepared by the present embodiment is more than 99%.

Embodiment 4

In the pending concentrated molybdenum ore of the present embodiment, the quality percentage composition of molybdenum is 50%, and the quality percentage composition of rhenium is 0.04%.In conjunction with Fig. 1, the present embodiment method of hydrometallurgical recovery molybdenum and rhenium from concentrated molybdenum ore comprises the following steps:

Step 1, concentrated molybdenum ore powder is mixed by solid-to-liquid ratio with deionized water at 1: 8, obtain ore pulp;

Step 2, under oxygen atmosphere, utilize autoclave to carry out pressure oxidation treatment to ore pulp described in step 1, the temperature of described pressure oxidation treatment is 210 ℃, and the time of described pressure oxidation treatment is 1.5h, and the pressure of described pressure oxidation treatment is 0.7MPa; After pressure oxidation treatment, concentrated molybdenum ore is mainly oxidized to molybdic oxide and proceeds to solid phase, and part molybdenum exists and proceed to liquid phase with molybdate form.There is and proceed to liquid phase with rehenic acid root form in whole rhenium elements.In concentrated molybdenum ore mainly there is and proceed to liquid phase with iron ion, cupric ion, lead ion form in the impurity such as the iron mineral of association, copper mineral, lead minerals;

Step 3, the ore pulp after pressure oxidation treatment in step 2 is carried out to filtration treatment, obtain filter cake and filtrate; In specific implementation process, can use deionized water repeatedly to rinse filter cake, the molybdate of adsorbing in filter cake and rehenic acid root be cleaned and entered in filtrate;

Step 4, filter cake described in step 3 and filtrate are processed respectively:

The treating processes of described filter cake is: filter cake is carried out to drying treatment, obtain industrial molybdenum oxide after naturally cooling;

The treating processes of described filtrate is:

Step 401, employing Sodium sulfhydrate carry out to remove impurity by means of precipitation processing to filtrate, be 7 until make the pH value of filtrate, make copper, iron, plumbous plasma precipitation in filtrate complete, then adopt the method for filtering by throw out reject, making the filtrate after to remove impurity by means of precipitation is the solution that only contains molybdate, rehenic acid root;

The ammoniacal liquor that step 402, employing mass percent concentration are 28% is adjusted to 9.5 by the pH value of the filtrate after to remove impurity by means of precipitation in step 401, be that to add pH value be in 9.5 filtrate to-100 orders~+ 200 object gac again by granularity, in order to the rhenium element in absorption filtrate, the add-on of described gac is in every liter of filtrate, to add 60g gac;

Step 403, employing are filtered, method centrifugal or sedimentation is carried out solid-liquid separation processing to the filtrate that is added with gac in step 402, then solid-liquid separation filtrate after treatment and gac are processed respectively:

Filtrate after treatment solid-liquid separation is carried out to crystallization treatment, obtain ammonium molybdate;

By solid-to-liquid ratio 1: 6, gac after treatment solid-liquid separation being added to temperature is to soak 3h in the deionized water of 60 ℃, the rhenium element solution that makes to be adsorbed on gac is drawn to liquid phase, because activated carbon surface can inevitably adhere to a small amount of ammonium radical ion, ammonium radical ion also can proceed in deionized water in immersion process, finally, by crystallization treatment, obtain ammonium perrhenate.

In industrial molybdenum oxide prepared by the present embodiment, the quality percentage composition of molybdenum is 53.42%, and the quality percentage composition 52.96% of the molybdenum wherein existing with molybdic oxide form is known as calculated, and the oxidation ratio of molybdenum is more than 99%.

In ammonium molybdate prepared by the present embodiment, the quality percentage composition of molybdenum is 54.9%.Known as calculated, the quality purity of ammonium molybdate prepared by the present embodiment is more than 95%.

In ammonium perrhenate prepared by the present embodiment, the quality percentage composition of rhenium is 69.40%.Known as calculated, the quality purity of ammonium perrhenate prepared by the present embodiment is more than 99%.

In the present invention, described solid-to-liquid ratio refers to the ratio of the quality of solid and the volume of liquid, and wherein the unit of solid masses is gram, and the unit of liquid volume is milliliter.

In the present invention, the granularity of described gac is-100 orders~+ 200 orders, refers to that the particle size of gac can be passed through 100 eye mesh screens, but can not pass through 200 eye mesh screens.Concrete preparation process is: activated carbon granule is crossed to 100 mesh sieve extracting screen underflows, then this screen underflow is crossed to 200 mesh sieves, get screen overflow, thereby obtain granularity for-100 orders~+ 200 object gac.

The above, be only preferred embodiment of the present invention, not the present invention imposed any restrictions.Every any simple modification of above embodiment being done according to invention technical spirit, change and equivalence change, and all still belong in the protection domain of technical solution of the present invention.

Claims (3)

1. a method for hydrometallurgical recovery molybdenum and rhenium from concentrated molybdenum ore, is characterized in that, the method comprises the following steps:
Step 1, by concentrated molybdenum ore powder and deionized water by solid-to-liquid ratio 1: (8~12) mix, and obtain ore pulp; In described concentrated molybdenum ore powder, the quality percentage composition of molybdenum is not less than 45%, and the quality percentage composition of rhenium is 0.02%~0.04%;
Step 2, under oxygen atmosphere, utilize autoclave to carry out pressure oxidation treatment to ore pulp described in step 1, the temperature of described pressure oxidation treatment is 180 ℃~210 ℃, the time of described pressure oxidation treatment is 1.5h~2h, and in pressure oxidation treatment process, the pressure of oxygen is 0.5MPa~0.7MPa;
Step 3, the ore pulp after pressure oxidation treatment in step 2 is carried out to filtration treatment, obtain filter cake and filtrate;
Step 4, filter cake described in step 3 and filtrate are processed respectively:
The treating processes of described filter cake is: filter cake is carried out to drying treatment, obtain industrial molybdenum oxide after naturally cooling;
The treating processes of described filtrate is:
Step 401, employing Sodium sulfhydrate carry out to remove impurity by means of precipitation processing to filtrate, are 7~8 rear filtering throw outs until make the pH value of filtrate;
Step 402, employing ammoniacal liquor are adjusted to 8.5~9.5 by the pH value of the filtrate after filtering throw out in step 401, then gac are added in the filtrate regulating after pH value and stir, in order to the rhenium element in absorption filtrate; The add-on of described gac is in every liter of filtrate, to add 50g~70g gac;
Step 403, the filtrate that is added with gac in step 402 is carried out to solid-liquid separation processing, then solid-liquid separation filtrate after treatment and gac is processed respectively, be specially:
Filtrate after treatment solid-liquid separation is carried out to crystallization treatment, obtain ammonium molybdate;
By solid-to-liquid ratio 1: it is to soak 1h~3h in the deionized water of 60 ℃~80 ℃ that gac after treatment solid-liquid separation is added temperature by (4~10), the rhenium element solution that makes to be adsorbed on gac is drawn in deionized water, then desorb there is is the deionized water of rhenium element to carry out crystallization treatment, obtain ammonium perrhenate.
According to claim 1 a kind of from concentrated molybdenum ore the method for hydrometallurgical recovery molybdenum and rhenium, it is characterized in that, the mass percent concentration of ammoniacal liquor described in step 402 is 25%~28%.
According to claim 1 a kind of from concentrated molybdenum ore the method for hydrometallurgical recovery molybdenum and rhenium, it is characterized in that, the granularity of gac described in step 402 is-100 orders~+ 200 orders.
CN201410120102.7A 2014-03-27 2014-03-27 Method of recycling molybdenum and rhenium from molybdenum concentrate by hydrometallurgy CN103866142A (en)

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CN106148732A (en) * 2015-03-27 2016-11-23 中南大学 A kind of process molybdenite and the method for bidery metal simultaneously
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CN106676267A (en) * 2017-03-28 2017-05-17 青岛阿库卡稀有金属有限公司 Method for removing anions from rhenium-contained feed liquid
CN107585789A (en) * 2017-09-26 2018-01-16 河南科技大学 A kind of method that high-purity molybdenum trioxide is prepared using hydrometallurgy molybdenum concntrate
CN107585789B (en) * 2017-09-26 2019-08-23 河南科技大学 A method of high-purity molybdenum trioxide is prepared using hydrometallurgy molybdenum concentrate
CN107746958A (en) * 2017-11-16 2018-03-02 福州大学 A kind of method that rhenium is reclaimed in the waste liquid from smelting
CN108193060A (en) * 2018-01-04 2018-06-22 中南大学 The method of rhenium-containing molybdenum concntrate volatilization-water logging separation molybdenum-rhenium
CN110592401A (en) * 2019-10-17 2019-12-20 西北有色金属研究院 Method for separating molybdenum and rhenium from rhenium-containing molybdenum concentrate oxidizing solution

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