CN101643245B - Process for preparing high-purity ammonium paratungstate - Google Patents

Process for preparing high-purity ammonium paratungstate Download PDF

Info

Publication number
CN101643245B
CN101643245B CN2008101348736A CN200810134873A CN101643245B CN 101643245 B CN101643245 B CN 101643245B CN 2008101348736 A CN2008101348736 A CN 2008101348736A CN 200810134873 A CN200810134873 A CN 200810134873A CN 101643245 B CN101643245 B CN 101643245B
Authority
CN
China
Prior art keywords
ammonium paratungstate
tungsten
tungstate solution
technology
exchange
Prior art date
Application number
CN2008101348736A
Other languages
Chinese (zh)
Other versions
CN101643245A (en
Inventor
余欢荣
李锦华
王光明
谢金明
肖健全
Original Assignee
江西稀有稀土金属钨业集团有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 江西稀有稀土金属钨业集团有限公司 filed Critical 江西稀有稀土金属钨业集团有限公司
Priority to CN2008101348736A priority Critical patent/CN101643245B/en
Publication of CN101643245A publication Critical patent/CN101643245A/en
Application granted granted Critical
Publication of CN101643245B publication Critical patent/CN101643245B/en

Links

Abstract

The invention relates to a process for preparing high-purity ammonium paratungstate, which can obtain a non-ferrous metal product, namely the ammonium paratungstate with low impurity content, wherein the impurity content of the ammonium paratungstate is low and is lower than 70 ppm, and the ammonium paratungstate can be directly used for preparing deep processed products of tungsten, such as tungsten powder with low impurity content and the like. The process comprises the following four process steps: (1) a process step of preparing a sodium tungstate solution by using a tungsten concentrate (Fe, Mn) WO4, white tungsten (CaWO4) or a tungsten middling product as a raw material; (2) a process step of performing ion exchange on the sodium tungstate solution; (3) a process step of performing impurity removal and filtration by using an ammonium tungstate solution; and (4) a process step of performing crystallization, washing, drying and screening. The process for preparing the high-purity ammonium paratungstate optimizes the technological processes, improves the quality of a product, and reduces the preparation cost of the product.

Description

A kind of technology of producing high-purity ammonium paratungstate
Technical field
The present invention relates to a kind of technology of producing ammonium paratungstate, particularly relate to a kind of technology of producing high-purity ammonium paratungstate.
In patent specification, term " high-purity ammonium paratungstate " is meant that total impurities can be controlled in the ammonium paratungstate within the 70ppm, i.e. the ammonium paratungstate of low impurity content, and GB zero level ammonium paratungstate product standard is total impurities≤177.5ppm.
So-called " ammonium paratungstate " also is called APT.
Term " sieve size " is by the above mineral granularity of-320 orders 〉=95% behind the ball milling.
Term " supernatant liquor that press filtration is come out " is coarse sodium tungstate, be through after the press filtration repeatedly coarse sodium tungstate.
Term " is handed over back liquid " and is meant the solution of discharging after sodium tungstate solution is through the ion exchange column adsorption operation.
What of tungstenic amount in the solution so-called " the tungstenic solution that desorbs divides three sections " be according to, and solution proportion makes a distinction.
Term " washing composition of washing " is the dilute ammonia solution with the 1%-3% of strong aqua and deionized water preparation.
Background technology
Tungsten is a kind of infusible non-ferrous metal, also is a kind of important strategic resource, because of premium propertiess such as it has the fusing point height, hardness is big, ductility is strong, wear-resisting and corrosion-resistant are used widely.
Along with the continuous development of tungsten industry, the ammonium paratungstate product of producing with existing ion exchange method only reaches GB zero level standard, more and more can not satisfy the needs of producing the tungsten deep processed product.As used ammonium para-tungstate crystal powder such as the deep processed product tungsten filament of now producing tungsten and tungsten alloy filaments, most of foreign matter content just must be less than 3 * 10 -5
The quality of ammonium paratungstate directly influences the quality of tungsten deep processed product, therefore will produce high-purity ammonium paratungstate and satisfy the needs that modern industry is produced.
Summary of the invention
The purpose of this invention is to provide a kind of technology of producing ammonium paratungstate, it can optimize technological process.
The purpose of this invention is to provide a kind of technology of producing high-purity ammonium paratungstate, it can obtain the ammonium paratungstate of low impurity content.
For this reason, the invention provides a kind of technology of producing high-purity ammonium paratungstate, it is with tungsten concentrate (Fe, Mn) WO 4, white tungsten (CaWO 4) or tungsten ore be raw material, have the sodium tungstate solution of producing operation; The ion-exchange process of sodium tungstate solution; Operation is filtered in the ammonium tungstate solution removal of impurities; Crystallizing and washing, oven dry, screening operation is characterized in that: in the ion-exchange process of sodium tungstate solution, by improving absorption, saturated charging is carried out in single-column ion-exchange; Adopt selectivity string post ion exchange method adsorption operation, in handing over back liquid, directly discharge during no tungsten, when having tungsten to contain WO in the liquid after the friendship 3During>0.2g/L, receive, seal in another exchange column and reclaim, saturated charging when resin absorption tungsten reaches working capacity with the transfer storage tank.
Preferably, ball milling, alkali cooking process add a certain amount of microcosmic salt (Na simultaneously 3PO 4), the microcosmic salt (Na that the soda boiling decomposition course adds 3PO 4) amount be to decide according to Ca content situation in the raw material.
Preferably, in producing the sodium tungstate solution operation simultaneously by adopting measures such as multistage heavy clear, press filtration, filtration.
Preferably, in the ion-exchange process of sodium tungstate solution, after drip washing is intact, open the draining of exchange column bottom valve, employing is fallen the liquid level desorption method and is fallen the liquid level operation, when liquid level is reduced to resin layer, uses 5NNH 4Cl+2NNH 4The OH mixed solution is made strippant, with the WO that adsorbs on the resin 4 2-Again desorb is got off.
Preferably, filter in the operation, the ammonium tungstate solution after the removal of impurities is strengthened sinking clearly, carried out filtration of multilayer filter cloth and Depth Filtration, remove the suspended matter in the ammonium tungstate solution in the ammonium tungstate solution removal of impurities.
Preferably, in the crystallizing and washing operation, with the weak ammonia detergent washing of the 1%-3% that prepared 1-3 time, after use deionized water wash 2-3 time again, produce the wet ammonium paratungstate of low impurity content.
Preferably, described ammonium paratungstate is controlled according to processing condition, makes content of impurities be controlled within the 70ppm.
Preferably, in the ion-exchange process of sodium tungstate solution, on the basis of single-column ion-exchange in the past and string post ion exchange technique,, saturated charging is carried out in single-column ion-exchange by improving absorption; Adopt selectivity string post ion exchange method adsorption operation, in handing over back liquid, directly discharge during no tungsten, when having tungsten to contain WO in the liquid after the friendship 3During>0.2g/L, receive, seal in another exchange column and reclaim, saturated charging when resin absorption tungsten reaches working capacity with the transfer storage tank.
Preferably, multistage heavy clear, the multilayer filter cloth filters and Depth Filtration is implemented by a kind of cylinder of filling resin.
Preferably, washing composition is the dilute ammonia solution with the 1%-3% of strong aqua and deionized water preparation.
According to the present invention, because with tungsten concentrate (Fe, Mn) WO 4, white tungsten (CaWO 4) or tungsten ore be raw material, add additive, guaranteed the decomposition effect; Then,,, strengthen the filtration of various solution by improving operating method such as absorption, drip washing, desorb by the saturated charging of single-column of ion-exchange, heavy clear measure, the optimization solution imbibition divides measure raising ammonium tungstate solution quality such as segment process.On the basis of original " selective precipitation method " impurity removing technology, the ammonium tungstate solution that the ion exchange process desorb is obtained carries out further removal of impurities, guarantees the ammonium tungstate solution quality by cascade filtrations such as multistage clarification and the filtration of multilayer filter cloth, Filter column Depth Filtrations; Primary crystallization terminal point to ammonium tungstate solution density is that 1.04~1.10g/Ml (contains WO 340~80g/L), the cooling blowing.In time crystal is separated with mother liquor by the disk vacuum filter during blowing, and with the detergent washing that has prepared 1-3 time, after use deionized water wash 2-3 time again; Can obtain the ammonium paratungstate of total impurities less than 70PPM high purity, high-performance low impurity content; Adopt the ammonium paratungstate of this low impurity content can further prepare the tungsten powder of low impurity content, improve the technology content and the added value of product of subsequent product.
To brief description of drawings
Fig. 1 is a schematic flow sheet of producing the technology of ammonium paratungstate according to of the present invention.
Fig. 2 is a schematic flow sheet of producing sodium tungstate solution in the technology of producing ammonium paratungstate according to the present invention.
Fig. 3 is the schematic flow sheet of the ion exchange process of sodium tungstate solution in the technology of producing ammonium paratungstate according to the present invention.
Fig. 4 is the schematic flow sheet of ammonium tungstate solution removal of impurities filtration procedure in the technology of producing ammonium paratungstate according to the present invention.
Fig. 5 is the schematic flow sheet of crystallizing and washing process in the technology of producing ammonium paratungstate according to the present invention.
Fig. 6 is the proof of technique effect: the ammonium paratungstate foreign matter content contrast table of zero level ammonium paratungstate and low impurity content.
Embodiment
Shown in Fig. 1-5,, be with wolframite (Fe, Mn) WO according to the technology of producing the Zhong Gaochun ammonium tungstate of the present invention 4, white tungsten (CaWO 4) or tungsten ore be raw material, key step comprises:
One, produces the coarse sodium tungstate operation
(1) tungsten minerals 10,21 is inserted in the ball mill feed bin, quantitatively at the uniform velocity tungsten minerals is sent in the vibromill by screw feeder, add an amount of microcosmic salt and water 221 simultaneously, carry out ball milling 11,22 fine grindings, make the tungsten minerals sieve size behind the ball milling reach-320 order 〉=95%, ore pulp solution 23 behind the ball milling adds: sheet alkali (NaOH) 241, alkali consumption are not less than 1.8 times of theoretical amount, preferred 2.1 times; Microcosmic salt (Na 3PO 4) 241, microcosmic salt (Na 3PO 4) amount be to decide according to Ca content situation in the raw material; And a certain amount of nitre 241, ore pulp is adjusted to certain volume, squeeze in the reactor, carry out soda boiling 11,24 and decompose reaction formula:
(Fe,Mn)WO 4+2NaOH=Na 2WO 4+(Fe,Mn)(OH) 2
CaWO 4+2NaOH=Ca(OH) 2+Na 2WO 4
3Ca(OH) 2+2Na 3PO 4=Ca 3(PO 4)+6NaOH
To the reactor heating, the alkali decomposition temperature is controlled at (preferred about 130 ℃) about 120 ℃-180 ℃; Pressure 0.5-1.1Kgf/cm 2(preferred 0.7Kgf/cm 2), be incubated 1.5-2 hour after (preferred 2 hours), put in the dilution bucket 25 that adds entry and a certain amount of tertiary sodium phosphate 251 in advance and dilute.
(2) in the dilution bucket, thin up is to 2-6 times (preferred 5 times) of original volume, the slag liquid entrance pressure filter press filtration of dilution back, washing, by a press filtration 26 back coarse sodium tungstate 27 is separated with filter-press residues 210 after the decomposition, the coarse sodium tungstate that a press filtration is come out carries out the secondary press filtration again, the solution of secondary press filtration is secondary press filtration coarse sodium tungstate 28, be three press filtrations afterwards, the sodium tungstate solution that three press filtrations are come out has reached the supernatant liquor that press filtration comes out and has been coarse sodium tungstate 12,29.
Two, the ion-exchange 13 purification and impurity removal operations of coarse sodium tungstate
(1) coarse sodium tungstate 31 that three press filtrations are got adds an amount of water 311 and dilutes, just obtained rare coarse sodium tungstate 32 of suitable ion-exchange process, when rare coarse sodium tungstate enters the ion exchange column from top to bottom from capital, resin in the post and the tungsten in the sodium tungstate solution adsorb reaction formula:
2R 4NCL+Na 2WO 4→(R 4N) 2WO 4+Na 2C1
(2) when sodium tungstate solution constantly flows into exchange column, begin to carry out the saturated absorption 33 of ion-exchange, because WO 4 2-Big with the avidity of resin, along with WO 4 2-Continuous increase, former other impurity negatively charged ion that is adsorbed on the resin at this moment will be by WO 4 2-Replace and discharge outside the exchange column, this process using selectivity string post ion exchange method adsorption operation promptly contains WO in the liquid after handing over 3≤ 0.2g/L (no tungsten is handed over back liquid liquid) directly was disposed to wastewater treatment 332 at 331 o'clock, and liquid contains WO after handing over 3>0.2g/L (tungstenic is handed over back liquid) 333, receive with the transfer storage tank, sealing in another exchange column reclaims, saturated charging when resin absorption tungsten reaches working capacity, stop to feed sodium tungstate solution, the saturated absorption of ion-exchange is finished, with deionized water wash tungsten 34 operations, when effluent liquid with advance post pure water PH near the time, one section liquid using circulating desorption acquisition carries out drip washing 34 operations as eluent, after drip washing is intact, carry out desorb 35 operations, open the draining of exchange column bottom valve and fall the liquid level operation, when liquid level is reduced to resin layer, use 5NNH 4Cl+2NNH 4OH mixed solution 351 is made strippant, with the WO that adsorbs on the resin 4 2-Again desorb is got off, and reaction formula is:
(R 4N) 2WO 4+NH 4CL→R 4NCL+(NH 4) 2WO 4
According to solution proportion, be tungstenic what, stripping liquid is carried out segmentation, the tungstenic solution that desorbs is general to divide three sections, one section liquid 36 tungstenic amount is hanged down and is returned eluent usefulness, and two sections high ammonium tungstate solutions of liquid 37 tungstenics send in next process, three sections liquid 38 tungstenics are low, chlorion and impurity level are low, return the preparation strippant and use.
Three, operation 14 is filtered in the ammonium tungstate solution removal of impurities
(1) the high ammonium tungstate solution 41 of tungstenic that will obtain is above sent into deblending slot, adopt " selective precipitation method " molybdenum removing technology, regulator solution PH is in 7-10 (preferred 9), add a certain amount of ammonium sulfide, copper sulfate 411 impurity removal reagents, the ammonium tungstate solution that the ion exchange process desorb is obtained carries out further removal of impurities, removes impurity such as molybdenum in the ammonium tungstate solution, arsenic, tin, antimony.
(2) to the ammonium tungstate solution after the removal of impurities strengthen heavy clear, carry out the multilayer filter cloth and filter 42 and Filter column Depth Filtration 43, remove the suspended matter in the ammonium tungstate solution, obtain the ammonium tungstate solution 44 after the removal of impurities.
Four, ammonium tungstate solution evaporative crystallization 15 washing procedures 16
(1) with the ammonium tungstate solution after the above-mentioned removal of impurities 51 through natures heavy clear, the multilayer filter cloth filters and Depth Filtration after, join in the crystallizing pan, carry out evaporative crystallization, the crystallisation process reaction formula:
12 (NH 4) 2WO 4→ 5 (NH 4) 2O12WO 35H 2O+14NH 3+ 2H 2O is in 90~120 ℃ (preferred 105 ℃) heating evaporation crystallization 52 down, and vapor pressure is controlled at 0.5~2.0Kgf/cm 3(preferred 1.5Kgf/cm 3), keep the about 10.50~14.50kPa of vacuum tightness during crystallization, to quicken the discharge of ammonia in the solution.
(2) when crystallization terminal point to ammonium tungstate solution density be 1.04~1.10g/mL (preferred 1.04g/mL), behind the naturally cooling 0.5~1.0 hour (preferred 1.0 hours).Open the bottom of a pan valve and carry out blowing, in time crystal is separated with mother liquor by the disk vacuum filter during blowing, and with the weak ammonia detergent washing for preparing 1%-3% (preferred 3%) 1-3 time (preferred 1 time), after use deionized water wash 2-3 time (preferred 3 times) (shown in 521 among Fig. 5) again, the high-purity ammonium paratungstate 17,54 that can obtain to wet behind the filtration washing 53.
(3) oven dry, screening 18 are put into the bipyramid dryer with the truck ammonium paratungstate that will wet, and start vacuum system and bipyramid dryer, logical drying with steam 55, and vapour pressure is controlled at 1~3Kgf/cm 2(preferred 2Kgf/cm 2), treat that material reaches dry the requirement after, stop to heat, keep 5-30 minute (preferred 10 minutes) of running, shut down, blowing enters and sieves 55 operations in the vibratory screening apparatus, sieve number is generally 80~120 orders (preferred 80 orders), can obtain high-purity ammonium paratungstate product 19,56 after the screening.Ammonium tungstate solution 110,57 after the crystallization (promptly mother liquor, contain WO 3But the generally wet ammonium paratungstate product 112,59 of 40~80g/L) secondary crystals, 111,58 outputs.Can obtain general ammonium paratungstate product 114,511 by operations such as above oven dry, screenings 113,510 equally.(secondary mother liquid contains WO to rare ammonium tungstate solution 115,512 3Less than 10g/L) turn back to and produce the coarse sodium tungstate operation.
In Fig. 6, embody very obviously according to the contrast between the foreign matter content of the ultrapure ammonium paratungstate of prepared of the present invention and zero level ammonium paratungstate.

Claims (8)

1. technology of producing ammonium paratungstate is with wolframite (Fe, Mn) WO 4, white tungsten (CaWO 4) or tungsten ore be raw material, it is characterized in that: have ion-exchange process, the ammonium tungstate solution removal of impurities of producing sodium tungstate solution operation, sodium tungstate solution and filter operation, crystallizing and washing, oven dry, screening operation, in the ion-exchange process of sodium tungstate solution, by improving absorption, saturated charging is carried out in single-column ion-exchange; In handing over back liquid, directly discharge during no tungsten, and when having tungsten to contain WO in the liquid after the friendship 3During>0.2g/L, receive, seal in another exchange column and reclaim, reach working capacity until resin absorption tungsten with the transfer storage tank; Filter in the operation in the ammonium tungstate solution removal of impurities, filtration of multilayer filter cloth and Filter column Depth Filtration are strengthened sinking clearly, carried out to the ammonium tungstate solution after the removal of impurities;
The content of impurities of described ammonium paratungstate is controlled within the 70ppm.
2. the technology of producing ammonium paratungstate according to claim 1 is characterized in that: in producing the sodium tungstate solution operation, when tungsten minerals being inserted in the ball mill feed bin, add an amount of Na 3PO 4At pressure-filtering process, adopt multistage press filtration, heavy clear measure simultaneously.
3. the technology of producing ammonium paratungstate according to claim 1 is characterized in that: in the ion-exchange process of sodium tungstate solution, after drip washing is intact, open the draining of exchange column bottom valve, employing is fallen the liquid level desorption method and is fallen the liquid level operation, when liquid level is reduced to resin layer, uses 5NNH 4Cl+2NNH 4The OH mixed solution is made strippant, with the WO that adsorbs on the resin 4 2-Again desorb is got off.
4. the technology of producing ammonium paratungstate according to claim 1 is characterized in that: produce in the sodium tungstate solution operation, ball milling, soda boiling decomposition course add Na 3PO 4Amount be to decide according to the content of calcium in the raw material (Ca).
5. the technology of producing ammonium paratungstate according to claim 1 is characterized in that: adopt selectivity string post ion-exchange absorption operation.
6. the technology of producing ammonium paratungstate according to claim 1 is characterized in that: the ammonium tungstate solution removal of impurities is filtered in the operation, and Depth Filtration is to implement by a kind of cylinder of filling resin.
7. the technology of producing ammonium paratungstate according to claim 1 is characterized in that: the washing composition in the crystallizing and washing operation is with the dilute ammonia solution about the 1%-3% of strong aqua and deionized water preparation.
8. the technology of producing ammonium paratungstate according to claim 1 is characterized in that: in the crystallizing and washing operation, with the weak ammonia detergent washing of the 1%-3% that prepared 1-3 time, after use deionized water wash 2-3 time again.
CN2008101348736A 2008-08-05 2008-08-05 Process for preparing high-purity ammonium paratungstate CN101643245B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008101348736A CN101643245B (en) 2008-08-05 2008-08-05 Process for preparing high-purity ammonium paratungstate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008101348736A CN101643245B (en) 2008-08-05 2008-08-05 Process for preparing high-purity ammonium paratungstate

Publications (2)

Publication Number Publication Date
CN101643245A CN101643245A (en) 2010-02-10
CN101643245B true CN101643245B (en) 2011-11-30

Family

ID=41655338

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008101348736A CN101643245B (en) 2008-08-05 2008-08-05 Process for preparing high-purity ammonium paratungstate

Country Status (1)

Country Link
CN (1) CN101643245B (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102154547B (en) * 2011-03-14 2013-01-16 崇义章源钨业股份有限公司 Method for decomposing scheelite with ammonium salts
CN104909408B (en) * 2012-12-25 2016-07-27 江西稀有金属钨业控股集团有限公司 Produce Application way and the system of waste heat in APT process
CN103950982B (en) * 2014-04-08 2016-02-17 崇义章源钨业股份有限公司 Ion exchange method prepares the method for ammonium paratungstate
CN104445416A (en) * 2014-11-12 2015-03-25 崇义章源钨业股份有限公司 Preparation method of uniform sodium-doped ammonium paratungstate and/or yellow tungsten oxide
CN104803417B (en) * 2015-05-06 2016-08-31 崇义章源钨业股份有限公司 Ammonium paratungstate and preparation method thereof
CN105197997B (en) * 2015-09-11 2017-01-04 中国有色集团(广西)平桂飞碟股份有限公司 The method of ammonium paratungstate degree of depth clarification
CN106582273A (en) * 2016-12-14 2017-04-26 衡阳市南东有色金属有限公司 Ammonium paratungstate production cycle weak acid recycling system
CN106731568A (en) * 2016-12-14 2017-05-31 衡阳市南东有色金属有限公司 Ammonium paratungstate production efficient circulation strong acid weak acid recovery processing system
CN106731598A (en) * 2016-12-14 2017-05-31 衡阳市南东有色金属有限公司 Ammonium paratungstate production efficient circulation strong acid recovery and processing system
CN106731569A (en) * 2016-12-14 2017-05-31 衡阳市南东有色金属有限公司 Ammonium paratungstate production efficient circulation weak acid recovery processing system
CN106693635A (en) * 2016-12-14 2017-05-24 衡阳市南东有色金属有限公司 Strong acid and weak acid recycling system during ammonium paratungstate production
CN107447119B (en) * 2017-07-14 2019-08-23 中南大学 A method of removing antimony, molybdenum, arsenic and tin from tungstate solution
CN108913884B (en) * 2018-07-23 2019-12-17 中国有色集团(广西)平桂飞碟股份有限公司 Method for preparing crude sodium tungstate solution by decomposing wolframite concentrate at low alkali and high temperature and pressure
CN109019690B (en) * 2018-09-13 2020-07-03 江西省科学院应用物理研究所 Short-process preparation method of rare earth doped modified ammonium paratungstate powder
CN109796046A (en) * 2019-03-20 2019-05-24 江西省鑫盛钨业有限公司 A kind of preparation process of high-purity ammonium paratungstate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115513A (en) * 1977-08-16 1978-09-19 Westinghouse Electric Corp. Processing of ammonium paratungstate from tungsten ores
CN1045958A (en) * 1989-03-31 1990-10-10 吉林锗厂 Ion exchange method prepares pure ammonium paratungstate method
CN1084575A (en) * 1993-07-13 1994-03-30 中南工业大学 Ion-exchange one-stage separation of phosphorus, arsenic, silicon, molybdenum are produced the technology of pure ammonium tungstate
CN1210894A (en) * 1996-04-02 1999-03-17 中南工业大学 Producing pure tungsten compound using tungsten-containing material
CN1377980A (en) * 2002-02-06 2002-11-06 王旭升 Process for preparing high purity ammonium para-tungstate using hihg-molybdenum tungsten ore

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115513A (en) * 1977-08-16 1978-09-19 Westinghouse Electric Corp. Processing of ammonium paratungstate from tungsten ores
CN1045958A (en) * 1989-03-31 1990-10-10 吉林锗厂 Ion exchange method prepares pure ammonium paratungstate method
CN1084575A (en) * 1993-07-13 1994-03-30 中南工业大学 Ion-exchange one-stage separation of phosphorus, arsenic, silicon, molybdenum are produced the technology of pure ammonium tungstate
CN1210894A (en) * 1996-04-02 1999-03-17 中南工业大学 Producing pure tungsten compound using tungsten-containing material
CN1377980A (en) * 2002-02-06 2002-11-06 王旭升 Process for preparing high purity ammonium para-tungstate using hihg-molybdenum tungsten ore

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
宁华.离子交换工艺在钨湿法冶炼中的应用.《工程设计与研究》.1997,(第95期),46-49. *
朱禹钧.用离子交换法提取仲钨酸铵.《铀矿冶》.1991,第10卷(第3期),39-47. *
魏庆玉.离子交换生产仲钨酸铵、三氧化钨、蓝色氧化钨的工艺与设备概述.《中国钨业》.1996,(第5期),8-11. *

Also Published As

Publication number Publication date
CN101643245A (en) 2010-02-10

Similar Documents

Publication Publication Date Title
CN104060295B (en) A kind of copper electrolyte absorption removing impurities purifying method
CN100420761C (en) Method for extracting rhenium from eluate of flue ash generated by baking enriched ore of molybdenum
DE112011101459T5 (en) A method of providing metallurgical grade aluminum using fluid bed ash
RU2454369C1 (en) Method of producing vanadium oxide
CN101973587B (en) Method for purifying ferrous sulfate heptahydrate byproduct in titanium white production
CA2574383C (en) Fluorine adsorbent/desorbent applicable in electrolytic solution for zinc electro-refining and method for removing fluorine using the fluorine adsorbent/desorbent
US4405569A (en) Hydrometallurgical process for extracting metal values from complex ores containing arsenic and sulfur
CN101186968A (en) Method for producing refined lithium sulfate solution used in lepidolite lithium-extracting technique by sulfuric acid process
CN102154565B (en) Method for extracting gallium from pulverized fuel ash
RU2478574C2 (en) Method of producing aluminium oxide from medium- and low-grade bauxite
RU2456241C2 (en) Method of producing vanadium oxide through extraction
CN85109224A (en) Gold recovery process
US9534273B2 (en) Alkaline and acid pressure oxidation of precious metal-containing materials
CN103924102B (en) Method for removing antimony from refractory gold ore and preparing cubic crystal sodium pyroantimonate
CN105349803B (en) A kind of method from the phosphotungstic acid containing molybdenum/phosphotungstate solution separation tungsten
CN100443601C (en) Method for producing metal gallium with coproduction of alumina
CN102191384B (en) Method for extracting gallium from fly ash
CN104831060B (en) A kind of method preparing oxide powder and zinc presoma zinc oxalate using middle-low grade zinc oxide ore
CN103979590B (en) A kind of method preparing high purity crystalline aluminum chloride
TWI594950B (en) A process, method and plant for recovering scandium
CN101880780B (en) Method for separating and extracting tungsten-molybdenum from mixed solution of tungstate-molybdate
US3981686A (en) Clarifier process for producing sodium carbonate
CN103194603A (en) Preparation method of high-purity vanadium pentoxide
US20190284659A1 (en) Precious metals recovery
US20130195737A1 (en) Method for extracting tungsten from scheelite

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
C14 Grant of patent or utility model