CN102978381B - 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
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- CN102978381B CN102978381B CN201210568936.5A CN201210568936A CN102978381B CN 102978381 B CN102978381 B CN 102978381B CN 201210568936 A CN201210568936 A CN 201210568936A CN 102978381 B CN102978381 B CN 102978381B
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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 waste residue that Wu Zhashi 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 tungsten raw ore by ore dressing is raw material, add additive, under High Temperature High Pressure alkaline condition, through Wet Decomposition or pyrogenic process, decompose, the waste residue that obtains the tungsten primary products such as sodium wolframate, calcium wolframate, ammonium paratungstate and fineness and be and be more than 100 orders is tungsten slag, one ton of WO of every output
3primary products are discharged approximately 0.8 ton of (residual WO simultaneously
31.5-6% tungsten slag; If adopt low tungsten concentrate, discharge the tungsten quantity of slag and relatively rise, conversion like this, China is annual more than 70,000 tons of the tungsten slags that produce at present, on average by residual WO
34% calculates, containing tungsten resource WO
3approximately 2800 tons, tungsten coin field is worth 5.5 hundred million yuan.Because tungsten slag has changed the chemical form of original physical structure or some component in smelting process, tungsten slag is difficult to by the method for ore dressing, reclaim again, at present, the utilization of domestic tungsten slag for comprehensive is generally to adopt traditional technology such as wet method, pyrogenic process or the coupling of wet method pyrogenic process again to reclaim in tungsten slag content at the WO below 3%
3time, have that energy consumption is high, 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 run off, cause the loss of approximately 30,000,000,000 yuan.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: comprise the following steps:
(1) will after the oven dry of tungsten slag, add hard coal, co-grinding, then add lime mud, sodium carbonate and water, and system ball dish ball processed, makes tungsten slag mixing bead, and wherein anthracitic addition is determined according to the thermal value of coal and maturing temperature, is 5 ~ 10% of tungsten slag amount,
(2) tungsten slag mixing bead being put into open hearth roasting kiln, is at 720 ~ 820 ℃, to carry out semi-enclosed insulation roasting at maturing temperature, cooling after roasting completes, then puts kiln blanking, obtains tungsten slag grog, and baking flue gas is emptying after three grades of sprays of NaOH solution;
(3) tungsten slag grog is packed into fermentation vat or soaking barrel and soak, obtain sodium wolframate mother liquor and waste residue, described sodium wolframate mother liquor obtains high density sodium wolframate mother liquor after ion-exchange;
(4) high density sodium wolframate mother liquor filters after magnesium salts method is except impurity such as dephosphorization silicon arsenic again, then adds calcium chloride or calcium hydroxide or calcium sulfate postprecipitation in filtrate, then throw out drip washing, dehydration, oven dry can be obtained to calcium wolframate product.
In step (1), tungsten slag mixing the small ball's diameter is 5 ~ 15mm.
In step (2), insulation roasting time is 2～6 h.
In step (2), the spray liquid of three grades of spray generations is made the ion regenerated liquid of ion-exchange.
10～20% ions of doing ion-exchange after adding NaOH to process of the waste water producing in precipitation process in the ion-exchange in step (3) and step (4) are freed liquid, interpolation water when all the other waste water are made ball processed in step 1.
In the flue gas that technique of the present invention produces when roasting, only has CO
2with a small amount of CO, SO
2, by can directly discharging after three grades of sprays of NaOH solution, ion regenerated liquid when produced simultaneously spray liquid can be done ion-exchange.Tungsten slag grog after roasting is after cold water soak, and sodium wolframate is soluble in water, leach liquor be 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, NaOH eluant solution tungsten for saturated resin, and high density sodium wolframate mother liquor is strengthened electrolyte purification and is removed the impurity such as silicon, phosphorus, arsenic.To the high density sodium wolframate mother liquor after filtering, add calcium chloride or calcium hydroxide or calcium sulfate again, generate CaWO
3precipitation, product can reach more than 70% artificial scheelite, and the resin after de-tungsten is regenerated with spray liquid, carries out next circulation absorption use transition.Part in the waste water of the waste water producing in the waste water producing when ion-exchange is adsorbed in the present invention, precipitation process, ion exchange resin conversion regeneration is made the ion of ion-exchange and is freed liquid after adding NaOH to process; 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 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 soda ash and burning expensive, that consumption is large used, 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, wet method pyrogenic process is produced upper energy efficient 50 percent.
Accompanying drawing explanation
Process flow sheet of the present invention in Fig. 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described, it should be understood that these embodiment, only for the object of illustration, never limit the scope of the invention.
As can be seen from Figure 1, the embodiment of the present invention adopts preparation technology as described below, specifically comprise the following steps: after 1, tungsten slag being dried, add hard coal, co-grinding, then add lime mud, sodium carbonate and water, system ball dish ball processed, make the tungsten slag mixing bead of diameter 5 ~ 15mm, wherein anthracitic addition is determined according to the thermal value of coal and maturing temperature, is 5 ~ 10% of tungsten slag amount
2, tungsten slag mixing bead being put into open hearth roasting kiln, is at 720 ~ 820 ℃, to carry out semi-enclosed insulation roasting 2～6h at maturing temperature, cooling after roasting completes, then puts kiln blanking, obtains tungsten slag grog, and baking flue gas is emptying after 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 and soak, obtain sodium wolframate mother liquor and waste residue, described sodium wolframate mother liquor obtains high density sodium wolframate mother liquor after ion-exchange,
4, high density sodium wolframate mother liquor filters after magnesium salts method is except the impurity such as dephosphorization silicon arsenic again, then to adding calcium chloride in filtrate or with calcium hydroxide and calcium sulfate postprecipitation, then throw out drip washing, dehydration, oven dry can be obtained to calcium wolframate product.
10～20% ions of doing ion-exchange after adding NaOH to process of the waste water wherein producing in ion-exchange and precipitation process are freed liquid, interpolation water when all the other waste water are made ball processed in 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 in above-described embodiment and specification sheets, describes 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. a technique for tungsten slag ball baked for producing processed tungstic oxide, is characterized in that: comprise the following steps:
(1) will after the oven dry of tungsten slag, add hard coal, co-grinding, then add lime mud, sodium carbonate and water, and system ball dish ball processed, makes tungsten slag mixing bead, and wherein anthracitic addition is determined according to the thermal value of coal and maturing temperature, is 5 ~ 10% of tungsten slag amount,
(2) tungsten slag mixing bead being put into open hearth roasting kiln, is at 720 ~ 820 ℃, to carry out semi-enclosed insulation roasting at maturing temperature, cooling after roasting completes, then puts kiln blanking, obtains tungsten slag grog, and baking flue gas is emptying after three grades of sprays of NaOH solution;
(3) tungsten slag grog is packed into fermentation vat or soaking barrel and soak, obtain sodium wolframate mother liquor and waste residue, described sodium wolframate mother liquor obtains high density sodium wolframate mother liquor after ion-exchange;
(4) high density sodium wolframate mother liquor filters except after dephosphorization silicon arsenic impurities through magnesium salts method again, then adds calcium chloride or calcium hydroxide or calcium sulfate postprecipitation in filtrate, then throw out drip washing, dehydration, oven dry can be obtained to calcium wolframate product.
2. technique according to claim 1, is characterized in that: in described step (1), tungsten slag mixing the small ball's diameter is 5 ~ 15mm.
3. technique according to claim 1, is characterized in that: in described step (2), insulation roasting time is 2～6 h.
4. technique according to claim 1, is characterized in that: in described step (2), the spray liquid of three grades of spray generations 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 NaOH to process of the waste water producing in precipitation process in the ion-exchange in step (3) and step (4) are freed liquid, interpolation water when all the other waste water are made the middle ball processed of step (1).
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN105463194B (en) * | 2015-12-04 | 2017-09-29 | 湖南金鑫新材料股份有限公司 | A kind of processing method of tungsten slag |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN110144466B (en) * | 2019-05-14 | 2021-07-20 | 荆门德威格林美钨资源循环利用有限公司 | Method for efficiently separating and recycling tungsten from alkaline leaching tungsten slag |
| CN110343857B (en) * | 2019-07-15 | 2021-03-23 | 厦门钨业股份有限公司 | Method for treating 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 |
| 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 |
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