CN113999978A - Method for recovering valuable metal from tungsten slag - Google Patents
Method for recovering valuable metal from tungsten slag Download PDFInfo
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- CN113999978A CN113999978A CN202111298250.4A CN202111298250A CN113999978A CN 113999978 A CN113999978 A CN 113999978A CN 202111298250 A CN202111298250 A CN 202111298250A CN 113999978 A CN113999978 A CN 113999978A
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- tungsten slag
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- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 79
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000010937 tungsten Substances 0.000 title claims abstract description 78
- 239000002893 slag Substances 0.000 title claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 44
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052718 tin Inorganic materials 0.000 claims abstract description 32
- 150000002739 metals Chemical class 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 16
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 14
- AHIVCQLQCIBVOS-UHFFFAOYSA-N [Fe].[W] Chemical compound [Fe].[W] AHIVCQLQCIBVOS-UHFFFAOYSA-N 0.000 claims abstract description 14
- RMOBRDQVMQCHCG-UHFFFAOYSA-N [Sn].[W].[Fe] Chemical compound [Sn].[W].[Fe] RMOBRDQVMQCHCG-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 239000002699 waste material Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 25
- 239000000956 alloy Substances 0.000 description 25
- 229910001145 Ferrotungsten Inorganic materials 0.000 description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- -1 tin metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/02—Obtaining tin by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明公开了一种从钨渣中回收有价金属的方法，所述方法包括：将钨渣和含碳物料按设定配比进行球磨混合得到预混合料；对所述预混合料进行高温还原，以得到钨铁锡合金；将所述钨铁锡合金进行真空蒸馏后得到钨铁合金和锡，后将所述钨铁合金和锡进行分离得到锡。本发明能有效的从钨渣中回收锡金属。The invention discloses a method for recovering valuable metals from tungsten slag. The method comprises: ball-milling and mixing tungsten slag and carbon-containing material according to a set ratio to obtain a premix; reduction to obtain tungsten-iron-tin alloy; vacuum distillation of the tungsten-iron-tin alloy to obtain tungsten-iron alloy and tin, and then separation of the tungsten-iron alloy and tin to obtain tin. The invention can effectively recover tin metal from tungsten slag.
Description
Technical Field
The invention relates to the technical field of pyrometallurgy, in particular to a method for recovering valuable metals from tungsten slag.
Background
Tungsten is a very important strategic metal, and China is the most abundant world in tungsten ore resource reserves, and the reserves account for about 47% of the total world reserves. The existing tungsten smelting process mainly adopts wet alkali treatment, but a large amount of tungsten alkali leaching slag (tungsten slag) is generated in the production process of the process. The accumulated tungsten slag in China reaches 100 ten thousand tons for years, and the speed of the accumulated tungsten slag is increased by nearly 8 ten thousand tons every year. The tungsten slag contains valuable metals such as W, Fe, Sn and the like, the valuable metals in the tungsten slag can be recovered to create larger economic value, the heavy metals in the tungsten slag are effectively prevented from polluting the environment, the social and economic benefits are remarkable, and the significance is great.
At present, valuable metals in tungsten slag are mainly recovered in two modes of a pyrogenic process and a wet process, and the pyrogenic process mainly adopts an alloy mode to recover the valuable metals in the tungsten slag. Realizing the recovery of valuable metals in the tungsten slag. And valuable metals in the tungsten slag are recovered by a wet method, the tungsten slag and 15% -25% hydrochloric acid are boiled and dissolved in acid, NaF and sodium nitrate are added, and after the reaction is finished, the valuable metals in the tungsten slag are recovered by filtering, extracting, evaporative crystallization and filter pressing.
However, neither the pyrogenic process nor the wet process can effectively recover tin metal from tungsten slag in the prior art, which results in waste of tin resources.
Disclosure of Invention
In view of the above, the present invention provides a method for recovering valuable metals from tungsten slag, and aims to recover tin metals from tungsten slag.
According to one embodiment of the invention, the method for recovering valuable metals from tungsten slag comprises the following steps:
carrying out ball milling mixing on tungsten slag and a carbon-containing material according to a set proportion to obtain a premix;
carrying out high-temperature reduction on the premix to obtain a tungsten-iron-tin alloy;
and carrying out vacuum distillation on the tungsten-iron-tin alloy to obtain the tungsten-iron alloy and tin, and then separating the tungsten-iron alloy and the tin to obtain the tin.
Preferably, when the tungsten slag and the carbon-containing material are subjected to ball milling and mixing, adding a ball milling additive;
wherein the ball milling additive comprises at least one of silicon dioxide and aluminum oxide.
Preferably, the carbon-containing material is carbon-containing waste, and the carbon-containing waste comprises at least one of negative electrode powder of a waste lithium battery and graphite powder recovered by molten salt electrolysis.
Preferably, 10-20 parts of carbon-containing material is added to 100 parts of tungsten slag.
Preferably, 10-15 parts of silicon dioxide and/or 4-9 parts of aluminum oxide are mixed in 100 parts of tungsten slag.
Preferably, the step of performing high temperature reduction on the premix to obtain the ferrotungsten-tin alloy comprises:
and carrying out compression molding on the premix, carrying out pre-roasting to obtain a tungsten slag blank, and carrying out high-temperature reduction on the tungsten slag blank to obtain the ferrotungsten-tin alloy.
Preferably, the process parameters of the ball milling are as follows: the rotation speed is 200r/min-300r/min, the time is 10-30min, and the forward and reverse rotation is switched every 5-10 min.
Preferably, the high-temperature reduction process is characterized in that the temperature is 1450-1650 ℃ and the time is 1-4 h.
Preferably, the process parameters of the vacuum distillation are as follows: the temperature of the heating zone is 1400-1700 ℃, the temperature of the condensation zone is 30-200 ℃, the vacuum degree is 0.1-200Pa, and the time is 1-4 h.
Preferably, the process parameters of the pre-roasting are as follows: the temperature is 350-500 ℃ and the time is 1-2 h.
Compared with the prior art: the invention realizes the recovery of the metallic tin in the tungsten slag by reducing the carbon-containing material and the tungsten slag to obtain the ferrotungsten alloy and the valuable metallic tin, and then separating the ferrotungsten alloy from the tin to obtain the tin metal.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. In the detailed description and claims, a list of items connected by the term "one of" may mean any of the listed items. For example, if items a and B are listed, the phrase "one of a and B" means a alone or B alone. In another example, if items A, B and C are listed, the phrase "one of A, B and C" means only a; only B; or only C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements. In the detailed description and claims, a list of items linked by the term "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" or "at least one of a or B" means a only; only B; or A and B. In another example, if items A, B and C are listed, the phrase "at least one of A, B and C" or "at least one of A, B or C" means a only; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.
The embodiment of the invention aims at the technical problem that valuable metal tin in tungsten slag cannot be effectively recovered at present, and particularly provides a method for recovering valuable metals from tungsten slag, wherein the method comprises the following steps:
carrying out ball milling mixing on tungsten slag and a carbon-containing material according to a set proportion to obtain a premix;
carrying out high-temperature reduction on the premix to obtain a tungsten-iron-tin alloy;
and carrying out vacuum distillation on the tungsten-iron-tin alloy to obtain the tungsten-iron alloy and tin, and then separating the tungsten-iron alloy and the tin to obtain the tin.
In some embodiments of the invention, a ball milling additive is added when the tungsten slag and the carbonaceous material are ball milled and mixed;
wherein the ball milling additive comprises at least one of silicon dioxide and aluminum oxide.
In some optional embodiments of the present invention, in order to increase the ball milling effect of the tungsten slag, two additives, namely silicon dioxide and aluminum oxide, are added simultaneously.
In some embodiments of the present invention, the carbon-containing material is carbon-containing waste material, and the carbon-containing waste material includes at least one of negative electrode powder of waste lithium battery and graphite powder recovered by molten salt electrolysis.
In some embodiments of the present invention, 10 to 20 parts of carbon-containing material, for example, 10 parts, 12 parts and 15 parts, is added to 100 parts of the tungsten slag.
In some embodiments of the present invention, 10 to 15 parts of silica and/or 4 to 9 parts of alumina, such as 13 parts of silica, 15 parts of silica and/or 4 parts of alumina and 7 parts of alumina, are added to 100 parts of tungsten slag.
In some embodiments of the invention, the step of reducing the premix at a high temperature to obtain the alloy comprises:
and carrying out compression molding on the premix, carrying out pre-roasting to obtain a tungsten slag blank, and carrying out high-temperature reduction on the tungsten slag blank to obtain the ferrotungsten-tin alloy.
In some embodiments of the invention, the process parameters of the ball milling are: rotating at 200r/min-300r/min for 10-30min, and switching between positive rotation and negative rotation every 5-10min, such as rotating at 200r/min for 10min, and switching between positive rotation and negative rotation every 5min to perform ball milling and mixing; the rotation speed is 240r/min, the time is 30min, and the ball milling and the mixing are switched between positive rotation and negative rotation at intervals of 10 min.
In some embodiments of the present invention, the temperature of the high temperature reduction process is 1450-; reducing at 1450 deg.C for 80 min.
In some embodiments of the present invention, the process parameters of the vacuum distillation are: the heating temperature is 1400-1700 ℃, the condensing temperature is 30-200 ℃, the vacuum degree is 0.1-200Pa, and the time is 1-4h, such as the heating temperature is 1600 ℃, the condensing temperature is 50 ℃, the vacuum degree is 50Pa, and the time is 3 h; the temperature of the heating zone is 1500 ℃, the temperature of the condensing zone is 150 ℃, the vacuum degree is 100Pa, and the time is 3 h.
In some embodiments of the present invention, the process parameters of the pre-baking are: the temperature is 350-500 ℃ and the time is 1-2 h, for example, the temperature is 500 ℃ and the time is 2 h; the temperature is 400 ℃ and the time is 2 h.
In order to facilitate an understanding of the invention, several embodiments of the invention are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
The method for recovering valuable metals from tungsten slag in the embodiment comprises the following steps:
adding 15 parts of carbon waste, 13 parts of silicon dioxide and 7 parts of aluminum oxide into 100 parts of tungsten slag, switching to ball milling and uniformly mixing in a forward and reverse rotation mode at the speed of 200r/min for 20min every 5min, pre-roasting the press-formed material at 500 ℃ for 2h, heating the pre-roasted material to 1550 ℃, and reducing for 70min to obtain a tungsten-iron alloy; and (3) carrying out vacuum distillation on the reduced ferrotungsten alloy for 3h at the heating zone temperature of 1600 ℃, the condensing zone temperature of 50 ℃ and the vacuum degree of 50Pa, and enriching and recovering valuable metal tin in the ferrotungsten alloy through a condensing tank.
Example 2
The method for recovering valuable metals from tungsten slag in the embodiment comprises the following steps:
adding 12 parts of carbon waste, 15 parts of silicon dioxide and 4 parts of aluminum oxide into 100 parts of tungsten slag, switching to positive and negative rotation at a rotation speed of 240r/min for 10min at intervals of 5min, ball-milling and uniformly mixing, pre-roasting the press-formed material at 400 ℃ for 2h, heating the pre-roasted material to 1450 ℃, and reducing for 70min to obtain a tungsten-iron alloy; and (3) carrying out vacuum distillation on the reduced ferrotungsten alloy for 3h at the temperature of 1500 ℃, the temperature of a condensation zone of 150 ℃ and the vacuum degree of 100Pa, and enriching and recovering valuable metal tin in the ferrotungsten alloy through a condensation tank.
Example 3
The method for recovering valuable metals from tungsten slag in the embodiment comprises the following steps:
adding 19 parts of carbon waste, 12 parts of silicon dioxide and 6 parts of aluminum oxide into 100 parts of tungsten slag, switching to ball milling and uniformly mixing in a forward and reverse rotation mode at the speed of 260r/min for 30min every 5min, pre-roasting the press-formed material for 1h at 450 ℃, heating the pre-roasted material to 1650 ℃, and reducing for 90min to obtain the tungsten-iron alloy; and (3) carrying out vacuum distillation for 3h at the temperature of 1600 ℃, the temperature of a condensation zone of 100 ℃ and the vacuum degree of 20Pa on the reduced ferrotungsten alloy, and enriching and recovering valuable metal tin in the ferrotungsten alloy through a condensation tank.
Example 4
The method for recovering valuable metals from tungsten slag in the embodiment comprises the following steps:
adding 12 parts of carbon waste, 13 parts of silicon dioxide and 7 parts of aluminum oxide into 100 parts of tungsten slag, switching to positive and negative rotation at a rotation speed of 280r/min for 20min at intervals of 10min, ball-milling and uniformly mixing, pre-roasting the press-formed material at 350 ℃ for 2h, heating the pre-roasted material to 1450 ℃, and reducing for 80min to obtain the ferrotungsten alloy; and (3) carrying out vacuum distillation for 1h at the temperature of 1400 ℃, the temperature of a condensation zone of 150 ℃ and the vacuum degree of 100Pa on the reduced ferrotungsten alloy, and enriching and recovering valuable metal tin in the ferrotungsten alloy through a condensation tank.
Example 5
The method for recovering valuable metals from tungsten slag in the embodiment comprises the following steps:
adding 14 parts of carbon waste, 13 parts of silicon dioxide and 5 parts of aluminum oxide into 100 parts of tungsten slag, switching to ball milling and uniformly mixing in a positive and negative rotation mode at a rotation speed of 200r/min for 30min every 10min, pre-roasting the press-formed material at 500 ℃ for 2h, heating the pre-roasted material to 1550 ℃, and reducing for 70min to obtain the tungsten-iron alloy; and (3) carrying out vacuum distillation on the reduced ferrotungsten alloy for 3h at the heating zone temperature of 1500 ℃, the condensing zone temperature of 50 ℃ and the vacuum degree of 50Pa, wherein valuable metal tin in the ferrotungsten alloy is enriched and recovered by a condensing tank, and the ferrotungsten alloy has no other impurities and high purity.
Example 6
The method for recovering valuable metals from tungsten slag in the embodiment comprises the following steps
Adding 13 parts of carbon waste, 12 parts of silicon dioxide and 7 parts of aluminum oxide into 100 parts of tungsten slag, switching to positive and negative rotation at a rotation speed of 280r/min for 15min at intervals of 5min, ball-milling and uniformly mixing, pre-roasting the press-formed material at 350 ℃ for 2h, heating the pre-roasted material to 1450 ℃, and reducing for 80min to obtain the ferrotungsten alloy; the reduced ferrotungsten alloy is subjected to vacuum distillation for 1h at the temperature of 1400 ℃, the temperature of a condensation zone of 150 ℃ and the vacuum degree of 90Pa, and valuable metal tin in the ferrotungsten alloy is enriched and recovered by a condensation tank
Example 7
The method for recovering valuable metals from tungsten slag in the embodiment comprises the following steps:
adding 17 parts of carbon waste, 12 parts of silicon dioxide and 6 parts of aluminum oxide into 100 parts of tungsten slag, switching to positive and negative rotation at a rotating speed of 240r/min for 25min at intervals of 5min, ball-milling and uniformly mixing, pre-roasting the press-formed material at 450 ℃ for 2h, heating the pre-roasted material to 1500 ℃, and reducing for 90min to obtain a tungsten-iron alloy; and (3) carrying out vacuum distillation for 1h at the temperature of 1400 ℃, the temperature of a condensation zone of 150 ℃ and the vacuum degree of 100Pa on the reduced ferrotungsten alloy, and enriching and recovering valuable metal tin in the ferrotungsten alloy through a condensation tank.
Example 8
The method for recovering valuable metals from tungsten slag in the embodiment comprises the following steps:
adding 15 parts of carbon waste, 10 parts of silicon dioxide and 4 parts of aluminum oxide into 100 parts of tungsten slag, switching to positive and negative rotation at a rotating speed of 230r/min for 30min at intervals of 6min, ball-milling and uniformly mixing, pre-roasting the press-formed material at 500 ℃ for 2h, heating the pre-roasted material to 1600 ℃, and reducing for 80min to obtain a tungsten-iron alloy; and (3) carrying out vacuum distillation for 2h at the temperature of 1500 ℃, the temperature of a condensation zone of 50 ℃ and the vacuum degree of 30Pa on the reduced ferrotungsten alloy, and enriching and recovering valuable metal tin in the ferrotungsten alloy through a condensation tank.
Referring to Table 1 below, the parameters for the above examples 1-8 of the present invention are shown in the following table.
Table 1:
in practical applications, the recovery rate of tin and ferrotungsten alloy prepared according to the above embodiments 1-8 of the present invention and the removal rate of tin from ferrotungsten alloy were respectively tested, and the test data are shown in table 2 below.
Table 2:
as is apparent from the data in tables 1 and 2, in the method for recovering valuable metals from tungsten slag according to the embodiment of the present invention, the tungsten slag and the carbonaceous material are reduced at a high temperature to obtain the wu-fe-sn alloy, and the tin is removed from the wu-fe-sn alloy by vacuum distillation, so that the tin in the tungsten slag can be effectively recovered.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
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| CN202111298250.4A CN113999978B (en) | 2021-11-04 | 2021-11-04 | Method for recovering valuable metals from tungsten slag |
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| CN113999978B CN113999978B (en) | 2023-06-30 |
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB306108A (en) * | 1928-02-16 | 1929-05-30 | Daniel Guggenheim | Treatment of tin-bearing materials |
| US4466826A (en) * | 1983-01-27 | 1984-08-21 | Ov-Eng Oy | Process for recovering metal values from alloy scraps |
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