RU2241051C1 - Method of processing molybdenum raw material - Google Patents

Method of processing molybdenum raw material Download PDF

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RU2241051C1
RU2241051C1 RU2003108902/02A RU2003108902A RU2241051C1 RU 2241051 C1 RU2241051 C1 RU 2241051C1 RU 2003108902/02 A RU2003108902/02 A RU 2003108902/02A RU 2003108902 A RU2003108902 A RU 2003108902A RU 2241051 C1 RU2241051 C1 RU 2241051C1
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Russia
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molybdenum
sorbent
solution
heavy metals
impurities
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RU2003108902/02A
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Russian (ru)
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RU2003108902A (en
Inventor
чко Л.И. Кл (RU)
Л.И. Клячко
нцев В.К. Рум (RU)
В.К. Румянцев
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Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский и проектный институт тугоплавких металлов и твердых сплавов"
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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

Abstract

FIELD: hydrometallurgy.
SUBSTANCE: method includes oxidizing breaking-down, filtering, and removing heavy metals from the molybdenum solution.
EFFECT: enhanced efficiency.
2 ex

Description

The invention relates to hydrometallurgy of molybdenum? in particular, the processing of molybdenum concentrates and waste.

There are two main methods for processing molybdenum raw materials.

A method of processing molybdenum raw materials is widely used in industrial practice, including oxidative calcination, leaching of the cinder with an ammonia solution, filtering and purification of the molybdenum solution from impurities of heavy metals. In this method, the cleaning of molybdenum solutions from iron, copper, etc., is carried out by their precipitation in the form of sulfides, adding ammonium hydrosulfide to the original ammonia solutions of molybdenum. Next, the resulting pulp is filtered. In this case, the sulfide precipitate contains a significant amount of molybdenum and rhenium, which must be extracted according to an additional technological scheme (Zelikman A.N. Metallurgy of refractory rare metals. - M .: Metallurgy, 1986, pp. 94-128).

The use of an additional technological scheme leads to significant losses of molybdenum and increases the production technological cycle.

Known hydrometallurgical methods for the decomposition of molybdenum raw materials in alkaline and acidic environments in the presence of an oxidizing agent and complexing agents. In one of these methods, the molybdenum feed is decomposed with nitric acid and filtered. The precipitate of molybdenum acid is directed to dissolve in ammonia water, and the mother liquor is sent to the additional recovery of molybdenum. This mother liquor is neutralized to pH 8-9 with ammonia water. In this case, all iron and partially molybdenum pass from a soluble state to a precipitate of ferromolybdate. After filtration, the sediment is stored, because there is no effective technology for its processing, or used for secondary purposes. And the mother liquor containing heavy metals and molybdenum is directed to the additional extraction of molybdenum.

After dissolution of the precipitate of molybdenum acid, along with the remainder of the undecomposed concentrate in 25% ammonia water, the resulting pulp is filtered. A solution containing molybdenum, rhenium and impurities is sent to purify heavy metal impurities. The precipitate is sent for re-opening and retrieval of molybdenum (A.N. Zelikman Metallurgy of refractory rare metals. - M .: Metallurgy, 1986, S. 129-141).

In addition, with the method of decomposition of molybdenum-containing raw materials by leaching in order to most fully convert molybdenum into soluble form, heavy metal salts are specially introduced into the pulp to form molybdenum-iron and molybdenum-copper heterocomplexes (AS 387600, MCP 22 22 49/00, 1973). The introduced impurities of these metals must also be removed from the process.

In the method of decomposition of molybdenum-containing raw materials (concentrates and metal waste) by decomposition with nitric acid, iron impurities are removed from the technological scheme in the form of precipitation of ferromolybdate salts, the processing of which is carried out according to a very complex technological scheme with large losses of molybdenum.

The closest technical solution is a method for processing molybdenum concentrates, including oxidative opening, filtering and contacting the resulting molybdenum solution with a macroporous vinyl-pyridine sorbent with the transition of molybdenum to the sorbent phase, further washing of the sorbent with water and desorption of molybdenum with an alkaline reagent (see RU 2017845, M, PCP 22 C 34/34, 08/15/1994).

This method provides for the multi-stage and duration of the process of processing molybdenum raw materials, which lead to additional losses of molybdenum, and also requires an additional operation for purification from impurities of heavy metals, which must be introduced into the technological scheme.

The present invention is to develop a method of processing molybdenum raw materials, providing a technical result, an increase in the extraction of molybdenum, improving the quality of purification of a solution of molybdenum from impurities of heavy metals and reducing the technological scheme of processing.

The technical result is achieved due to the fact that in the method of processing molybdenum raw materials, including oxidative opening, filtering, contacting the resulting molybdenum solution with a macroporous vinyl pyridine sorbent with the transition of molybdenum to the sorbent phase, washing the sorbent with water and desorbing the molybdenum with an alkaline reagent, according to the invention, contacting with the sorbent is carried out for 7-9 hours at a pH of 0.8-1.2 when cleaning molybdenum from impurities of heavy metals.

The feedstock - molybdenum concentrate or industrial waste is subjected to oxidative opening by known methods, filtering is carried out and solutions containing Mo and heavy metals such as Fe, Cu, Ni, etc. are obtained and the precipitate is sent to the dump. The molybdenum solution is neutralized to a pH of 0.8-1.2 and purified from impurities of heavy metals.

The cleaning is carried out by contacting the solution with a macroporous vinyl-pyridine sorbent for 7-9 hours. The sorbents used are weakly basic anion exchangers of the VP - 1P type, which have a macroporous structure and contain pyridine nitrogen as ionogenic groups. The advantage of anion exchangers is that they allow not only the separation of molybdenum and impurities of heavy metals, but also the conversion of molybdenum salts to the necessary ammonium molybdate (NH 4 ) 2 MoO 4 , from which commercial products are obtained: ammonium paramolybdate or molybdenum oxide.

The separation of molybdenum and heavy metals in solution occurs at a pH of 0.8-1.2. In the selected conditions in solutions containing molybdenum-iron and molybdenum-copper heterocomplexes [H 3 FeMo 6 O 21] and [H 4 SuMo 6 O 21] is their destruction and transition iron FeSO 4, copper - in CuSO 4, t .e. into cationic forms, which are not adsorbed by anion exchange resin, but molybdenum [Mo 7 O 6- 21 ] goes into the phase of the sorbent, from where it can be desorbed with any alkaline reagent, depending on the further purpose of the product.

If the solution has a pH of less than 0.8 or greater than 1.2, the molybdenum-iron and molybdenum-copper heterocomplexes are not susceptible to degradation in a strongly acidic environment and remain in solution.

The cleaning of the molybdenum solution by contacting with the sorbent is carried out for 7-9 hours. In this case, all impurities of heavy metals (Fe, Cu, Ni, etc.) remain in solution, and molybdenum passes into the sorbent phase. When cleaning the solution by contact with the sorbent for less than 7 hours, not all molybdenum has time to go into the sorbent phase, and cleaning with a duration of more than 9 hours is impractical, because the solution already practically contains only heavy metals and is then sent for recycling. And the sorbent is sent to extract molybdenum from it. There is no re-opening of sediment and additional recovery of molybdenum in the proposed technological process, which allows to reduce the loss of valuable metals and to reduce the technological scheme of the process.

Example 1. A solution of sodium polymolybdate was obtained from calcined molybdenum concentrate according to TU 48-19-354-82 by leaching the latter with sodium carbonate at pH 3-4 (according to known technology). The amount of solution is 150 ml. The solution was acidified to pH 0.8-1.2 with sulfuric acid (GOST 4204-77) according to a pH meter (pH-340) and stirred in a glass flask with a stirrer. The resulting sodium polymolybdate solution containing (g / l): Mo - 115; Fe - 2.76; Cu - 1.31 at pH 0.87 under static conditions was purified by contacting with 10 g of macroporous sorbent grade VP-1P grains of class A (0.63-1.6 mm), manufactured according to OST 95.291-75, TU 95.329-77 , for 7 hours. Received the capacity in the sorbent, mg / g: Mo 493; Fe 24.1; Cu 8.7. The sorbent was washed with water in an amount of 2 volumes per 1 volume of sorbent. As a result, the content of impurities in the sorbent (mg / g) was obtained: Fe - 0.6; Cu - not detected.

The solution containing heavy metals, after washing, was sent for recycling, and the sorbent was used to extract molybdenum. After processing the sorbent with 3 volumes of a solution of 8% ammonia (TU 6-09-3282-73), the solution turned out to be (g / l): Mo - 114.77; Cu and Fe - not detected. Thus, the recovery of Mo was 99.8%. The residual capacity of the sorbent, mg / g: Mo 12; Fe 0.6; Cu - no. Thus, almost complete separation of molybdenum and impurities of heavy metals occurs.

Example 2. Molybdenum-containing solution was obtained after opening the molybdenum concentrate in accordance with GOST 212-76 with nitric acid in accordance with GOST 4461-77 in the presence of an oxidizing agent - technical oxygen (95% O 2 ) at T: W = 1: 4 and t = 90-100 ° С for 4 hours in a machine with mechanical stirring, after control filtration on a filter press, the solution was neutralized to a pH of 0.8 - 1.2 by adding a 25% ammonia solution according to TU 6-09-3282-73 by a pH meter (pH 340). Stock solution containing, g / l: Mo 5.98; Fe 1.34; Cu 1,2, was purified by contacting with a sorbent of the grade VP-1P grains in class A (0.63-1.6 mm) according to OST 95.291-75, TU 95.327-77 in SO -2 4 - form. The weight of the sorbent is 10 g, the volume of the solution is 500 ml, the duration of purification by contacting with the sorbent is 9 hours. The sorbent capacity was (mg / g): Mo - 264; Fe and Cu - chemical analysis is not detected. In the waste solution, which is sent for disposal, chemical analysis revealed the content, g / l: Mo 0.03; Fe 1.3; Cu 1,2. Molybdenum was recovered from the sorbent in the same manner as in Example 1. 99.7% molybdenum recovery.

Thus, the proposed technical solution ensures the reduction of known operations of the technological cycle by eliminating the repeated operations of opening and cleaning from impurities of heavy metals of the main technological solution. As a result of the creation of continuous production, it becomes possible to automate processes and replace hard physical labor of workers. This reduces the cost of raw materials, basic and auxiliary materials (mainly reagents), increases the extraction of molybdenum to 97-99%, depending on the selected technology for processing molybdenum concentrates. In addition, the amount of harmful substances entering the wastewater is reduced, therefore, the cost of their disposal is reduced.

Claims (1)

  1. A method of processing molybdenum raw materials, including oxidative opening, filtering, contacting the resulting molybdenum solution with a macroporous vinyl pyridine sorbent with the transition of molybdenum to the sorbent phase, washing the sorbent with water and desorbing the molybdenum with an alkaline reagent, characterized in that the contact with the sorbent is carried out for 7-9 h at pH 0.8-1.2, when cleaning molybdenum from impurities of heavy metals.
RU2003108902/02A 2003-04-01 2003-04-01 Method of processing molybdenum raw material RU2241051C1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2475549C1 (en) * 2011-10-26 2013-02-20 Закрытое акционерное общество Научно-производственное предприятие "Промтех" (ЗАО НПП "Промтех") Extraction method of molybdenum trioxide from tailings
RU2529142C1 (en) * 2013-02-20 2014-09-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Забайкальский государственный университет" (ФГБОУ ВПО "ЗабГУ") Method for removing molybdenum from man-made mineral formations
RU2536615C1 (en) * 2013-08-19 2014-12-27 Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) Method for processing of sulphide and mixed molybdenum-containing concentrates
RU2703757C1 (en) * 2019-04-10 2019-10-22 Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) Method of processing sulphide and mixed molybdenum-containing concentrates

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2475549C1 (en) * 2011-10-26 2013-02-20 Закрытое акционерное общество Научно-производственное предприятие "Промтех" (ЗАО НПП "Промтех") Extraction method of molybdenum trioxide from tailings
RU2529142C1 (en) * 2013-02-20 2014-09-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Забайкальский государственный университет" (ФГБОУ ВПО "ЗабГУ") Method for removing molybdenum from man-made mineral formations
RU2536615C1 (en) * 2013-08-19 2014-12-27 Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) Method for processing of sulphide and mixed molybdenum-containing concentrates
RU2703757C1 (en) * 2019-04-10 2019-10-22 Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) Method of processing sulphide and mixed molybdenum-containing concentrates

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