CN102978381A - Technology for producing tungsten trioxide by prilling and roasting of tungsten slag - Google Patents
Technology for producing tungsten trioxide by prilling and roasting of tungsten slag Download PDFInfo
- Publication number
- CN102978381A CN102978381A CN2012105689365A CN201210568936A CN102978381A CN 102978381 A CN102978381 A CN 102978381A CN 2012105689365 A CN2012105689365 A CN 2012105689365A CN 201210568936 A CN201210568936 A CN 201210568936A CN 102978381 A CN102978381 A CN 102978381A
- Authority
- CN
- China
- Prior art keywords
- tungsten slag
- tungsten
- roasting
- slag
- mother liquor
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Images
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a technology for producing tungsten trioxide by prilling and roasting of tungsten slag. The technology is characterized by comprising the following steps of: (1) baking tungsten slag and then adding blind coal, mixing and crushing the tungsten slag and the blind coal, and then adding lime mud, sodium carbonate and water, priling in a priling disc to prepare the mixed tungsten slag balls; (2) putting the mixed tungsten slag balls into an open hearth kiln to carry out semi-enclosed insulated roasting so as to obtain a tungsten slag clinker; (3) soaking the tungsten slag clinker, and carrying out ion exchange to obtain high-concentration sodium tungstate mother liquor; (4) removing the impurity of the high-concentration sodium tungstate mother liquor, and then filtering, precipitating, leaching the sediment, dewatering and baking the sediment to obtain a calcium tungstate product. The tungsten slag, the blind coal, the lime mud and recycling wastewater are adopted as roasting agents to replace soda ash and burning acid with high price and large consumption for the traditional technology-wet firing method, so that the tungsten production cost of each metal ton is reduced by***, and the transformation rate of WO3 is improved by 25%; the chronic diseases of sodium-process rotary kiln roasting and caking shovel kiln stop production are successfully solved, and about 50% of energy consumption is saved on the traditional technology and wet firing production.
Description
Technical field
The present invention relates to a kind of technique of comprehensive reutilization of tungsten slag resource.
Background technology
The tungsten slag is the waste residue that tungsten smelting enterprise produces in the production process of pressure leaching.Pressure leaching process is that the standard tungsten concentrate of the content 65% that obtains after adopting the tungsten raw ore by ore dressing is raw material, add additive, under the High Temperature High Pressure alkaline condition, decompose through Wet Decomposition or pyrogenic process, obtaining the tungsten primary products such as sodium wolframate, calcium wolframate, ammonium paratungstate and fineness is that the above waste residue of 100 orders is the tungsten slag, one ton of WO of every output
3Primary products are discharged about 0.8 ton of (residual WO simultaneously
31.5-6% tungsten slag; If adopt low tungsten concentrate, then discharge the tungsten quantity of slag and relatively rise, like this conversion, China is annual more than 70,000 tons of the tungsten slags that produce at present, on average by residual WO
34% calculates, and contains tungsten resource WO
3About 2800 tons, tungsten coin field is worth 5.5 hundred million yuan.Because the tungsten slag has changed the chemical form of original physical structure or some component in smelting process, the tungsten slag is difficult to reclaim with the method for ore dressing again, at present, the utilization of domestic tungsten slag for comprehensive generally is to adopt traditional technology such as wet method, pyrogenic process or the coupling of wet method pyrogenic process again to reclaim in the tungsten slag content at the WO below 3%
3The time, have that energy consumption is high, the subsidiary material consumption is large, cost is high, there is no the problems such as economic benefit, so caused the comprehensive utilization ratio of tungsten slag not high, and tungsten slag for many years banked up in a large number naturally, not only caused serious environmental pollution and harm, also make a large amount of valuable metal resources cause waste and loss, cause about 30,000,000,000 yuan loss.The comprehensive recycling process technology of therefore researching and developing new tungsten slag resource is significant.
Summary of the invention
The comprehensive utilization ratio that the object of the invention is to propose a kind of tungsten slag is high, production cost is low, the technique of the tungsten slag ball baked for producing processed tungstic oxide of non-environmental-pollution.
The technical solution used in the present invention is: the technique of a kind of tungsten slag ball baked for producing processed tungstic oxide is characterized in that: may further comprise the steps:
(1) will add hard coal after the oven dry of tungsten slag, co-grinding adds lime mud, yellow soda ash and water again, and system ball dish ball processed is made tungsten slag mixing bead, and wherein anthracitic addition is decided according to thermal value and the maturing temperature of coal, is 5 ~ 10% of tungsten slag amount,
(2) tungsten slag mixing bead being put into the open hearth roasting kiln, is to carry out semi-enclosed insulation roasting under 720 ~ 820 ℃ at maturing temperature, and the kiln blanking is put in cooling after roasting is finished again, gets tungsten slag grog, and baking flue gas is emptying behind three grades of sprays of NaOH solution;
(3) tungsten slag grog is packed into fermentation vat or soaking barrel soaks, and gets sodium wolframate mother liquor and waste residue, described sodium wolframate mother liquor after ion-exchange high density sodium wolframate mother liquor;
(4) high density sodium wolframate mother liquor filters after the magnesium salts method is except impurity such as dephosphorization silicon arsenic again, adds calcium chloride or calcium hydroxide or calcium sulfate postprecipitation again in filtrate, again throw out drip washing, dehydration, oven dry can be got the calcium wolframate product.
Tungsten slag mixing the small ball's diameter is 5 ~ 15mm in the step (1).
The insulation roasting time is 2～6 h in the step (2).
The spray liquid of three grades of spray generations is made the ion regenerated liquid of ion-exchange in the step (2).
10～20% of the waste water that produces in the precipitation process in ion-exchange in the step (3) and the step (4) is freed liquid through adding the ions of doing ion-exchange after NaOH processes, the interpolation water when all the other waste water are made ball processed in the step 1.
Only has CO in the flue gas that technique of the present invention produces when roasting
2With a small amount of CO, SO
2, by can directly discharging the ion regenerated liquid when produced simultaneously spray liquid can be done ion-exchange behind three grades of sprays of NaOH solution.Tungsten slag grog after the roasting is after cold water soak, and sodium wolframate is soluble in water, leach liquor be the sodium wolframate mother liquor through loading capacity up to 720mg/g temperature resin, easy wash-out, regeneration drip washing is reliable.Good work environment easily is automated control, and the total yield of tungsten has improved more than 25 percentage points than traditional technology, and saturated resin is strengthened electrolyte purification and removed the impurity such as silicon, phosphorus, arsenic with NaOH eluant solution tungsten, high density sodium wolframate mother liquor.High density sodium wolframate mother liquor after filter adds calcium chloride or calcium hydroxide or calcium sulfate again, generates CaWO
3Precipitation, product can reach the artificial scheelite 70% or more, and the resin that takes off behind the tungsten is regenerated with spray liquid, carries out next circulation absorption use transition.Part in the waste water of the waste water that produces in the waste water that produces when ion-exchange is adsorbed in the present invention, the precipitation process, ion exchange resin conversion regeneration adds the ion of doing ion-exchange after NaOH processes and frees liquid; interpolation water when all the other waste water are made ball processed; accomplish wastewater zero discharge and reached reliable environment protection; take full advantage of sodium ions a large amount of in the waste water, greatly reduce again consumption and the production cost of additive.
It is sour that the present invention adopts tungsten slag, hard coal, lime mud and recycling waste water to make the alternative traditional technology one wet method pyrogenic process of calcination agent used soda ash and burning expensive, that consumption is large, make the tungsten production cost of each metal ton reduce by 6-7 ten thousand yuan, make the transformation efficiency of WO3 improve 25 percentage points, and successfully solved the roasting of sodium method rotary kiln, the persistent ailment that caking shovel kiln stops production, also in traditional technology, energy efficient 50 percent in the production of wet method pyrogenic process.
Description of drawings
Process flow sheet of the present invention among Fig. 1.
Embodiment
The present invention will be further described below in conjunction with drawings and Examples, it should be understood that these embodiment only are used for the purpose of illustration, never limit protection scope of the present invention.
As can be seen from Figure 1, the embodiment of the invention adopts preparation technology as described below, specifically may further comprise the steps: 1, will add hard coal after the oven dry of tungsten slag, co-grinding adds lime mud, yellow soda ash and water again, system ball dish ball processed, make the tungsten slag mixing bead of diameter 5 ~ 15mm, wherein anthracitic addition is decided according to thermal value and the maturing temperature of coal, is 5 ~ 10% of tungsten slag amount
2, tungsten slag mixing bead being put into the open hearth roasting kiln, is to carry out semi-enclosed insulation roasting 2～6h under 720 ~ 820 ℃ at maturing temperature, and the kiln blanking is put in cooling after roasting is finished again, gets tungsten slag grog, and baking flue gas is emptying behind three grades of sprays of NaOH solution; The spray liquid of three grades of spray generations is made the ion regenerated liquid of ion-exchange.
3, tungsten slag grog is packed into fermentation vat or soaking barrel soaks, and gets sodium wolframate mother liquor and waste residue, described sodium wolframate mother liquor after ion-exchange high density sodium wolframate mother liquor,
4, high density sodium wolframate mother liquor filters after the magnesium salts method is except impurity such as dephosphorization silicon arsenic again, adds calcium chloride or with calcium hydroxide and calcium sulfate postprecipitation, again throw out drip washing, dehydration, oven dry can be got the calcium wolframate product in filtrate again.
10～20% of the waste water that wherein produces in ion-exchange and precipitation process is freed liquid through adding the ions of doing ion-exchange after NaOH processes, the interpolation water when all the other waste water are made ball processed in the step 1.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention; the technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention, and the claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (5)
1. the technique of a tungsten slag ball baked for producing processed tungstic oxide is characterized in that: may further comprise the steps:
(1) will add hard coal after the oven dry of tungsten slag, co-grinding adds lime mud, yellow soda ash and water again, and system ball dish ball processed is made tungsten slag mixing bead, and wherein anthracitic addition is decided according to thermal value and the maturing temperature of coal, is 5 ~ 10% of tungsten slag amount,
(2) tungsten slag mixing bead being put into the open hearth roasting kiln, is to carry out semi-enclosed insulation roasting under 720 ~ 820 ℃ at maturing temperature, and the kiln blanking is put in cooling after roasting is finished again, gets tungsten slag grog, and baking flue gas is emptying behind three grades of sprays of NaOH solution;
(3) tungsten slag grog is packed into fermentation vat or soaking barrel soaks, and gets sodium wolframate mother liquor and waste residue, described sodium wolframate mother liquor after ion-exchange high density sodium wolframate mother liquor;
(4) high density sodium wolframate mother liquor filters after the magnesium salts method is except impurity such as dephosphorization silicon arsenic again, adds calcium chloride or calcium hydroxide or calcium sulfate postprecipitation again in filtrate, again throw out drip washing, dehydration, oven dry can be got the calcium wolframate product.
2. technique according to claim 1 is characterized in that: tungsten slag mixing the small ball's diameter is 5 ~ 15mm in the described step (1).
3. technique according to claim 1 is characterized in that: the insulation roasting time is 2～6 h in the described step (2).
4. technique according to claim 1 is characterized in that: the spray liquid that three grades of sprays produce in the described step (2) is made the ion regenerated liquid of ion-exchange.
5. technique according to claim 1, it is characterized in that: 10～20% ions of doing ion-exchange after adding the NaOH processing of the waste water that produces in the precipitation process in the ion-exchange in the step (3) and the step (4) are freed liquid, the interpolation water when all the other waste water are made the middle ball processed of step (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210568936.5A CN102978381B (en) | 2012-12-25 | 2012-12-25 | Technology for producing tungsten trioxide by prilling and roasting of tungsten slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210568936.5A CN102978381B (en) | 2012-12-25 | 2012-12-25 | Technology for producing tungsten trioxide by prilling and roasting of tungsten slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102978381A true CN102978381A (en) | 2013-03-20 |
| CN102978381B CN102978381B (en) | 2014-04-02 |
Family
ID=47852715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210568936.5A Expired - Fee Related CN102978381B (en) | 2012-12-25 | 2012-12-25 | Technology for producing tungsten trioxide by prilling and roasting of tungsten slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102978381B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834815A (en) * | 2014-03-25 | 2014-06-04 | 西北有色金属研究院 | Method of separating tungsten and tantalum in tantalum-containing tungsten-rich slag |
| CN105463194A (en) * | 2015-12-04 | 2016-04-06 | 湖南金鑫新材料有限公司 | Tungsten residue treatment method |
| CN106435224A (en) * | 2016-08-17 | 2017-02-22 | 湖南金源新材料股份有限公司 | Method for preparing ammonium paratungstate from waste containing tungsten |
| CN107385241A (en) * | 2017-07-03 | 2017-11-24 | 信丰华锐钨钼新材料有限公司 | A kind of Efficient utilization method of scheelite soda boiling slag |
| CN109402379A (en) * | 2018-10-17 | 2019-03-01 | 崇义章源钨业股份有限公司 | The method of tungstenic solid arsenic removal |
| CN109825725A (en) * | 2019-03-25 | 2019-05-31 | 湖南懋天世纪新材料有限公司 | A kind of method of comprehensive utilization of tungstenic causticization slag |
| CN109911941A (en) * | 2019-03-25 | 2019-06-21 | 湖南力天高新材料股份有限公司 | A method of extracting sodium tungstate from high silicon tungsten waste |
| CN110079664A (en) * | 2019-04-19 | 2019-08-02 | 崇义章源钨业股份有限公司 | The method of Tungsten smelting waste residue arsenic removal |
| CN110144466A (en) * | 2019-05-14 | 2019-08-20 | 荆门德威格林美钨资源循环利用有限公司 | A method of recycling tungsten is efficiently separated from alkali leaching tungsten slag |
| CN110343857A (en) * | 2019-07-15 | 2019-10-18 | 厦门钨业股份有限公司 | The method for handling tungsten ore |
| CN111057880A (en) * | 2019-12-27 | 2020-04-24 | 厦门钨业股份有限公司 | Method for recovering tungsten from tungsten-containing waste material |
| CN114380317A (en) * | 2021-10-24 | 2022-04-22 | 崇义章源钨业股份有限公司 | Method for recycling hydrochloric acid by recovering calcium sulfate from pickle liquor |
-
2012
- 2012-12-25 CN CN201210568936.5A patent/CN102978381B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 《中南工业大学学报（自然科学版)》 20030228 戴艳阳等 "钨渣中有价金属综合回收工艺" 第36-39页 1-5 第34卷, 第1期 * |
| 《科协论坛》 20091231 吕宁娟 "低品位钨渣的资源化利用" 第130页 1-5 , 第9期 * |
| 吕宁娟: ""低品位钨渣的资源化利用"", 《科协论坛》 * |
| 戴艳阳等: ""钨渣中有价金属综合回收工艺"", 《中南工业大学学报（自然科学版)》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834815A (en) * | 2014-03-25 | 2014-06-04 | 西北有色金属研究院 | Method of separating tungsten and tantalum in tantalum-containing tungsten-rich slag |
| CN103834815B (en) * | 2014-03-25 | 2016-01-20 | 西北有色金属研究院 | A kind of method be separated containing tungsten tantalum in the rich tungsten slag of tantalum |
| CN105463194A (en) * | 2015-12-04 | 2016-04-06 | 湖南金鑫新材料有限公司 | Tungsten residue treatment method |
| CN106435224A (en) * | 2016-08-17 | 2017-02-22 | 湖南金源新材料股份有限公司 | Method for preparing ammonium paratungstate from waste containing tungsten |
| CN106435224B (en) * | 2016-08-17 | 2019-01-25 | 湖南金源新材料股份有限公司 | The method for preparing ammonium paratungstate with tungsten waste |
| CN107385241A (en) * | 2017-07-03 | 2017-11-24 | 信丰华锐钨钼新材料有限公司 | A kind of Efficient utilization method of scheelite soda boiling slag |
| CN107385241B (en) * | 2017-07-03 | 2019-05-03 | 信丰华锐钨钼新材料有限公司 | A kind of Efficient utilization method of scheelite soda boiling slag |
| CN109402379A (en) * | 2018-10-17 | 2019-03-01 | 崇义章源钨业股份有限公司 | The method of tungstenic solid arsenic removal |
| CN109825725A (en) * | 2019-03-25 | 2019-05-31 | 湖南懋天世纪新材料有限公司 | A kind of method of comprehensive utilization of tungstenic causticization slag |
| CN109911941A (en) * | 2019-03-25 | 2019-06-21 | 湖南力天高新材料股份有限公司 | A method of extracting sodium tungstate from high silicon tungsten waste |
| CN110079664A (en) * | 2019-04-19 | 2019-08-02 | 崇义章源钨业股份有限公司 | The method of Tungsten smelting waste residue arsenic removal |
| CN110144466A (en) * | 2019-05-14 | 2019-08-20 | 荆门德威格林美钨资源循环利用有限公司 | A method of recycling tungsten is efficiently separated from alkali leaching tungsten slag |
| CN110343857A (en) * | 2019-07-15 | 2019-10-18 | 厦门钨业股份有限公司 | The method for handling tungsten ore |
| CN111057880A (en) * | 2019-12-27 | 2020-04-24 | 厦门钨业股份有限公司 | Method for recovering tungsten from tungsten-containing waste material |
| CN114380317A (en) * | 2021-10-24 | 2022-04-22 | 崇义章源钨业股份有限公司 | Method for recycling hydrochloric acid by recovering calcium sulfate from pickle liquor |
| CN114380317B (en) * | 2021-10-24 | 2023-10-24 | 崇义章源钨业股份有限公司 | Method for recycling hydrochloric acid by recovering calcium sulfate from pickle liquor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102978381B (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102978381B (en) | Technology for producing tungsten trioxide by prilling and roasting of tungsten slag | |
| CN103849774B (en) | A kind of method that discarded SCR catalyst is recycled | |
| CN103194603B (en) | Preparation method of high-purity vanadium pentoxide | |
| CN100560757C (en) | A kind of process for extracting vanadium by stone coal wet method | |
| CN109336140B (en) | Process for extracting lithium by adding lithium iron phosphate into lepidolite | |
| CN107299223B (en) | A kind of compound alkaline-leaching and vanadium extraction method of bone coal and its system | |
| CN101503762B (en) | Desulphurization and vanadium extraction technique for calcinated vanadium ore | |
| CN101230419A (en) | Method for extracting vanadium pentoxide and comprehensively extracting ammonium alum and iron-oxide red from vanadium-containing stone coal or vanadium-containing ash slag | |
| CN104528834B (en) | Artificial rutile mether liquor recycling novel method | |
| CN107619941A (en) | The method that vanadium and chromium are separated from vanadium chromium slag | |
| CN100580107C (en) | Method for extracting vanadic anhydride from stone coal vanadium ore | |
| CN104561540A (en) | Method for selectively leaching serpentine type laterite-nickel ores by utilizing hydrochloric acid | |
| CN104261473B (en) | A kind of preparation method of Vanadium Pentoxide in FLAKES | |
| CN102923774B (en) | Method for adding high-calcium vanadium slag to perform sodium salt roasting | |
| CN102260801B (en) | Clean conversion method of stone coal | |
| CN102718267B (en) | Method for preparing black iron oxide by utilizing yellow ammonium iron alum slag | |
| CN112267023A (en) | Two-stage defluorination method for fluorine-containing material | |
| CN103014321B (en) | Raw material pretreatment process for extracting vanadium from vanadium slag | |
| CN107574308B (en) | A kind of method of Manganese anode slime manganese lead separation | |
| CN106676275A (en) | Vanadium extraction method based on waste steel slag and acid-base property waste water | |
| CN101358301A (en) | Method for directly extracting vanadium from vanadium titan magnetite concentrate | |
| CN104294033A (en) | Vanadium extracting process for silicate type vanadium ore | |
| CN108516569A (en) | The method that lepidolite roasting prepares lithium sulfate solution | |
| CN110395751A (en) | A method of lithium sulfate is extracted from lepidolite | |
| CN102534232A (en) | Method for decomposing vanadium slag under normal pressure by adding carbon-containing substance into sodium hydroxide solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140402 Termination date: 20191225 |