CN108796226B - A method of it recycling alkali and soaks tungsten slag - Google Patents
A method of it recycling alkali and soaks tungsten slag Download PDFInfo
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- CN108796226B CN108796226B CN201810726170.6A CN201810726170A CN108796226B CN 108796226 B CN108796226 B CN 108796226B CN 201810726170 A CN201810726170 A CN 201810726170A CN 108796226 B CN108796226 B CN 108796226B
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- 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
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- 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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- 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
- C22B43/00—Obtaining mercury
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- 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
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- 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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Abstract
The present invention provides a kind of method of recycling alkali leaching tungsten slag, the present invention carries out pre-burning reduction after mixing alkali leaching tungsten slag with reducing agent, is collected simultaneously the heavy metal of volatilization, obtains primary slag and heavy metal alloy；The heavy metal alloy is a variety of in As, Pb and Hg；Smelting reduction is carried out after obtained primary slag is mixed with slag former obtains secondary slag and ferroalloy.Acid is not used in method of the invention, reduces pollution；Obtained ferroalloy can be directly used for potassium steel or the intermediate alloy of other special steels uses；The content of beary metal in secondary slag generated after tungsten slag secondary reduction is less than 100ppm, reaches national environmental standard, can stack naturally, or for fields such as road construction, mine filling and devitrified glasses.
Description
Technical field
The present invention relates to metallurgical technology field, in particular to a kind of method for recycling alkali leaching tungsten slag.
Background technique
There is the most abundant tungsten ore resource in the world in China, while being also the big producer of ammonium paratungstate (APT), and APT is raw
A large amount of solid waste, the tungsten slag mainly generated after tungsten concentrate soda boiling are generated during producing.Since the normal association of tungsten concentrate is some
Heavy metal (such as As, Pb, Hg), these heavy metals eventually enter into tungsten slag.Since tungsten smelting process changes mineral physics knot
The chemical form of structure and certain components, and it is mixed into CO3 2-、PO4 3-、F-Plasma, make tungsten slag composition and each side's surface properties compared with
For complexity, tungsten slag is caused to be difficult to be recycled with physical upgrading method again.Utilize traditional wet process, pyrogenic process or wet process-pyrogenic process etc.
Technology recycling wherein valuable metal when the problems such as that there are cost recovery is high, deficiency in economic performance, so as to cause the comprehensive utilization of tungsten slag
Rate is very low.And a large amount of tungsten slags do not only take up a large amount of soils by unordered stacking, water system, soil and atmosphere are caused seriously to pollute and
Harm；It efficiently use a large amount of valuable metal resource cannot, cause waste and the stream of tungsten and other valuable metal resources
It loses.According to statistics, the generation coefficient of tungsten slag is about 0.8, i.e., it is left that every production 1t tungsten primary product (sodium tungstate, APT) will generate 0.8t
Right tungsten slag, there are about 60,000 tons of tungsten slag mucks to deposit every year in the whole nation, and decades produce the cumulative tungsten slag more than million tons and do not make to locate
Reason.Therefore, the comprehensive reutilization for studying tungsten slag is of great significance.
Chinese patent CN103290224A discloses a kind of recovery process of valuable metal in tungsten slag, by tungsten slag and 15%~
It is molten that 25% hydrochloric acid boils acid, and NaF is added, and sodium nitrate filters to get filtrate after the reaction was completed；Then filtrate is extracted
Crystallization obtains APT；Alkali soluble is carried out to filter residue, Ta, Nb, Sn valuable metal are directly recycled in filters pressing.Although the method can synthetical recovery portion
Divide valuable metal, but not can solve the heavy metal pollution problem of the dangerous wastes element such as As, Pb, Hg in tungsten slag.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of method of recycling alkali leaching tungsten slag, side provided by the invention
Method can a variety of valuable metal elements in synthetical recovery tungsten slag, and solve the heavy metal pollution problem of As, Pb and Hg in tungsten slag.
The present invention provides a kind of methods of recycling alkali leaching tungsten slag, comprising the following steps:
1) pre-burning reduction is carried out after mixing alkali leaching tungsten slag with reducing agent, is collected simultaneously the heavy metal of volatilization, is obtained primary
Slag and heavy metal alloy；The heavy metal alloy is a variety of in As, Pb and Hg；
2) smelting reduction is carried out after the primary slag for obtaining step 1) is mixed with slag former obtains secondary slag and ferroalloy.
Preferably, the reducing agent in the step 1) includes carbon, ferrosilicon, manganese iron, calcium carbide, silico-calcium, magnesium, aluminium or rare earth gold
Belong to.
Preferably, the mass ratio of the alkali leaching tungsten slag and reducing agent in the step 1) is 3~30:1.
Preferably, the temperature of step 1) the pre-burning reduction is 500~1200 DEG C, and the time of the pre-burning reduction is 0.1
~3h.
Preferably, in the step 2) slag former include one of calcium oxide, aluminium oxide, calcium hydroxide and dolomite or
It is several.
Preferably, the mass ratio of the primary slag in the step 2) and slag former is 3~50:1.
Preferably, the temperature of smelting reduction is 1400~1600 DEG C in the step 2), time of smelting reduction is 0.5~
5h。
Preferably, the content of As, Pb and Hg are respectively lower than 100ppm in secondary slag in told step 2).
Preferably, ferroalloy is made of the element of following mass percentage in the step 2):
Manganese 5~30%
The total content 1~5% of tungsten and niobium
Remaining is iron.
Advantageous effects: the present invention provides a kind of method of recycling alkali leaching tungsten slag, alkali is soaked tungsten slag by the present invention
Pre-burning reduction is carried out after mixing with reducing agent, is collected simultaneously the heavy metal of volatilization, is obtained primary slag and heavy metal alloy；It is described heavy
Metal alloy is a variety of in As, Pb and Hg；Smelting reduction is carried out after primary slag is mixed with slag former obtains secondary slag and iron
Alloy.The present invention uses pre-burning reducing process, recycles heavy metal element As, Pb and Hg in tungsten slag, and it is dirty to solve tungsten residue heavy metal
Dye problem, while can tentatively restore iron oxide and tungsten oxide in tungsten slag；Using smelting reducing process, after pre-burning can be restored
Valuable metal element smelting reduction in tungsten slag is ferroalloy, and promotes reduction and the slag gold point of tungsten slag by addition slag former
From.Acid is not used in the present invention, reduces pollution；And obtained ferroalloy purity with higher, and contain more manganese (5
~30%) and a small amount of tungsten and niobium (1~5%), the intermediate alloy that can be directly used for potassium steel or other special steels use,
Economic value with higher；The content of beary metal in secondary slag generated after tungsten slag secondary reduction is less than 100ppm, reaches state
Family's environmental protection standard, can stack naturally, or for fields such as road construction, mine filling and devitrified glasses.
Specific embodiment
The present invention provides a kind of methods of recycling alkali leaching tungsten slag, comprising the following steps:
1) pre-burning reduction is carried out after mixing alkali leaching tungsten slag with reducing agent, is collected simultaneously the heavy metal of volatilization, is obtained primary
Slag and heavy metal alloy；The heavy metal alloy is a variety of in As, Pb and Hg；
2) smelting reduction is carried out after the primary slag for obtaining step 1) is mixed with slag former, obtains secondary slag and ferroalloy.
The present invention carries out pre-burning reduction after mixing alkali leaching tungsten slag with reducing agent, is collected simultaneously the heavy metal of volatilization, obtains
Primary slag and heavy metal alloy；The heavy metal alloy is a variety of in As, Pb and Hg.
In the present invention, the alkali leaching tungsten slag is preferably the tungsten generated after tungsten concentrate soda boiling in ammonium paratungstate generating process
Slag.
In the present invention, the reducing agent preferably includes carbon, ferrosilicon, manganese iron, calcium carbide, silico-calcium, magnesium, aluminium or rare earth gold
Belong to.
In the present invention, the mass ratio of the alkali leaching tungsten slag and reducing agent is preferably 3~30:1, and more preferably 10~25:
1, most preferably 15~20:1.
The method that the present invention mixes alkali leaching tungsten slag with reducing agent is not particularly limited, and selects those skilled in the art known
Mixed method.In the present invention, it is preferred to which the method using ball milling is mixed.
The present invention is not particularly limited the granularity after ball milling, selects granularity well known to those skilled in the art.
The present invention is not particularly limited the method for ball milling, selects method well known to those skilled in the art.
In the present invention, the temperature of the pre-burning reduction is preferably 500~1200 DEG C, and more preferably 800~1000 DEG C, institute
The time for stating pre-burning reduction is preferably 0.1~3h, more preferably 0.5~2.5h, most preferably 1.5~2h.The present invention preferably from
Room temperature is to pre-burning reduction temperature, and the heating rate is preferably 5~30 DEG C/min, more preferably 10~30 DEG C/min, most
Preferably 20~30 DEG C/min.
The present invention uses pre-burning reducing process, recycles heavy metal element As, Pb and Hg in tungsten slag, solves tungsten residue heavy metal
Pollution problem, while can tentatively restore iron oxide and tungsten oxide in tungsten slag.
The device that the present invention restores pre-burning is not particularly limited, and selects device well known to those skilled in the art,
In the present invention, it is preferred to using tunnel atmosphere furnace.
In the present invention, it is preferred to which the heavy metal that will volatilize condenses to obtain heavy metal alloy.
In the present invention, the temperature of the condensation is preferably 0~200 DEG C, and more preferably 5~50 DEG C.
In the present invention, the heavy metal alloy can be used as producing the raw material of arsenic, lead, mercury elemental metals.
In the present invention, the alkali leaching tungsten slag preferably carries out drying and processing before pre-burning restores.
In the present invention, the temperature of the drying and processing is preferably 80~300 DEG C, and more preferably 100~200 DEG C；It is described
The time of drying and processing is preferably 2~12h, more preferably 4~8h.
The present invention is not particularly limited the method for drying and processing, selects furnace drying method well known to those skilled in the art i.e.
Can, it is preferably carried out by way of baking oven or flame baking in the present invention.
The present invention removes the low-melting impurities such as moisture and the greasy filth in tungsten slag by drying and processing.
After obtaining primary slag, the present invention carries out smelting reduction after mixing obtained primary slag with slag former, obtains secondary
Slag and ferroalloy.
In the present invention, the slag former preferably include one of calcium oxide, aluminium oxide, calcium hydroxide and dolomite or
It is several, more preferably calcium oxide and aluminium oxide.In the present invention, when slag former is two or more mixture, the present invention couple
The proportion of each slag former is not particularly limited in mixture, is mixed with arbitrary proportion.
In the present invention, the mass ratio of the primary slag and slag former is preferably 3~50:1, more preferably 10~40:1,
Most preferably 20~30:1.
The method that the present invention mixes primary slag with slag former is not particularly limited, and is selected well known to those skilled in the art
Mixed method.In the present invention, it is preferred to be mixed with the method for ball milling.
The present invention is not particularly limited the granularity after the ball milling, selects granularity well known to those skilled in the art i.e.
It can.
The present invention is not particularly limited the method for ball milling, selects method well known to those skilled in the art.
The present invention promotes the reduction of tungsten slag to separate with slag gold by addition slag former.
In the present invention, the temperature of the smelting reduction is preferably 1400~1600 DEG C, and more preferably 1450~1550 DEG C；
The time of the smelting reduction is preferably 0.5~5h, more preferably 1~4h, most preferably 2~3h.Heating rate is preferably 1~
30 DEG C/min, more preferably 5~15 DEG C/min
The present invention is not particularly limited the device of smelting reduction, selects device well known to those skilled in the art.
The present invention is preferably vacuum induction melting furnace.
In the present invention, the content of As, Pb and Hg are independently preferably less than 100ppm in the secondary slag, more preferably
Lower than 80ppm.
In the present invention, the secondary slag can directly be stacked or for road construction, mine filling or devitrified glass
Equal fields.
In the present invention, the ferroalloy alloy is preferably made of the element of following mass percentage:
Manganese 5~30%
The total content 1~5% of tungsten and niobium
Remaining is iron.
The ferroalloy that the present invention obtains can be directly used for potassium steel or the intermediate alloy of other special steels uses.
In the present invention, after the smelting reduction, preferably cold to high temperature reduction reaction solution progress furnace or casting of coming out of the stove is obtained
Ferroalloy and secondary slag.
The present invention is cold to furnace, and the concrete operations with casting of coming out of the stove are not particularly limited, and select art technology arbitrarily well known
Operation.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
Tungsten slag derives from domestic ammonium paratungstate (APT) manufacturing enterprise
Dry tungsten slag 200g, carbon dust 30g, calcium oxide 15g, aluminium oxide 10g are weighed, ball milling mixing is placed on alumina crucible
In, pre-burning reduction is carried out in tunnel atmosphere furnace.Pre-burning reducing process are as follows: 900 DEG C of the low-temperature zone heat preservations 0.5 first in continuous tunnel furnace
Hour, As, Pb, Hg heavy metal of low-temperature zone reduction volatilization in collection obtain heavy metal alloy by condensation；Subsequently enter high temperature
1450 DEG C of heat preservation 1h of section carry out the reaction of tungsten slag smelting reduction and the separation of slag gold, and subsequent furnace is cold, is cooled to room temperature, comes out of the stove, and obtains
Ferroalloy productor and secondary slag.By carrying out weighing and composition detection to ferroalloy, the results are shown in Table 1, as shown in Table 1,
Iron yield reaches 96.78%, and manganese yield reaches 61.96%, and tungsten yield reaches 71.85%, Nb yield and reaches 73.21, which closes
Gold can be used for preparing the intermediate alloy raw material of steel alloy.Toxicity characteristic leaching procedure is carried out to secondary slag, as a result reaches national environmental protection mark
It is quasi-.
Each component content table of comparisons in the tungsten slag of reduction front and back in 1 embodiment 1 of table
Embodiment 2
Dry tungsten slag 1000g, carbon dust 150g are weighed, ball milling is mixed, is subsequently placed in alumina crucible, in box atmosphere furnace
Carry out pre-burning reduction.Reducing process are as follows: 860 DEG C keep the temperature 1 hour, then furnace cooling.Reduction process leads to nitrogen protection, in atmosphere
The exhaust outlet of furnace collects As, Pb, Hg heavy metal of reduction process volatilization by condensation, obtains heavy metal alloy.Also by atmosphere furnace
Primary slag after original takes out, and adds slag former calcium oxide 70g, aluminium oxide 50g, after ball milling mixes, briquet.Then 5
Smelting reduction is carried out in feather weight vacuum induction melting furnace, melting kettle uses high purity graphite crucible, and smelting temperature control exists
1500 DEG C~1550 DEG C, melting 5min is kept the temperature, subsequent tapping casting obtains ferroalloy ingot casting and secondary slag.By to ferroalloy
Weighing and composition detection are carried out, the results are shown in Table 2, and as shown in Table 2, iron yield reaches 95.72%, and manganese yield reaches
68.33%, tungsten yield reaches 73.48%, Nb yield and reaches 70.56, which can be used for preparing the intermediate alloy of steel alloy
Raw material.Toxicity characteristic leaching procedure is carried out to secondary slag, as a result reaches national environmental standard.
Each component content table of comparisons in the tungsten slag of reduction front and back in 2 embodiment 2 of table
Embodiment 3
Dry tungsten slag 500g is weighed, carbon dust 80g is weighed, ball milling is mixed, is subsequently placed in alumina crucible, in box atmosphere furnace
Middle progress pre-burning reduction.Reducing process are as follows: 900 DEG C keep the temperature 0.5 hour, then furnace cooling.Reduction process leads to nitrogen protection, In
The exhaust outlet of atmosphere furnace collects As, Pb, Hg heavy metal of reduction process volatilization by condensation, obtains heavy metal alloy.By atmosphere
Primary slag after furnace reduction takes out, and adds slag former calcium oxide 40g, aluminium oxide 25g, after ball milling mixes, briquet.Then
The smelting reduction in vacuum carbon tube furnace.Reducing process are as follows: 1550 DEG C of heat preservation 1.5h, carry out tungsten slag final stage reduction reaction with
And the separation of slag gold, subsequent furnace is cold, is cooled to room temperature, comes out of the stove, and obtains ferroalloy productor and secondary slag.By claiming to ferroalloy
Weight and composition detection, the results are shown in Table 3, and as shown in Table 3, iron yield reaches 98.25%, and manganese yield reaches 67.18%, tungsten
Yield reaches 73.47%, Nb yield and reaches 80.22%, which can be used for preparing the intermediate raw material of steel alloy.To secondary slag
Toxicity characteristic leaching procedure is carried out, national environmental standard is as a result reached.
Each component content table of comparisons in the tungsten slag of reduction front and back in 3 embodiment 3 of table
Embodiment 4
Dry tungsten slag 500g is weighed, carbon dust 30g is weighed, ball milling is mixed, is subsequently placed in alumina crucible, in box atmosphere furnace
Middle progress pre-burning reduction.Reducing process are as follows: 1200 DEG C keep the temperature 0.1 hour, then furnace cooling.Reduction process leads to nitrogen protection,
As, Pb, Hg heavy metal that reduction process is volatilized are collected by condensation in the exhaust outlet of atmosphere furnace, obtain heavy metal alloy.By gas
Primary slag after the reduction of atmosphere furnace takes out, and adds reducing agent silicon calcium powder 80g and slag former calcium hydroxide 30g, after ball milling mixes, pressure
Block is made.The then smelting reduction in vacuum carbon tube furnace.Reducing process are as follows: 1600 DEG C of heat preservation 0.5h carry out the last rank of tungsten slag
Section reduction reaction and the separation of slag gold, subsequent furnace is cold, is cooled to room temperature, comes out of the stove, and obtains ferroalloy productor and secondary slag.By right
Ferroalloy carries out weighing and composition detection, and the results are shown in Table 5, and as shown in Table 5, iron yield reaches 97.28%, and manganese yield reaches
To 66.39%, tungsten yield reaches 73.29%, Nb yield and reaches 77.73%, which can be used for preparing the centre of steel alloy
Raw material.Toxicity characteristic leaching procedure is carried out to secondary slag, as a result reaches national environmental standard.
Each component content table of comparisons in the tungsten slag of reduction front and back in 4 embodiment 4 of table
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of method for recycling alkali leaching tungsten slag, comprising the following steps:
1) pre-burning reduction is carried out after mixing alkali leaching tungsten slag with reducing agent, the heavy metal that will volatilize in pre-burning reduction process is cold
It is solidifying, obtain primary slag and heavy metal alloy；The heavy metal alloy is a variety of in As, Pb and Hg；The temperature of the pre-burning reduction
Degree is 500~1200 DEG C；
2) smelting reduction is carried out after the primary slag for obtaining step 1) is mixed with slag former, obtains secondary slag and ferroalloy.
2. the method according to claim 1, wherein the reducing agent in the step 1) includes carbon, ferrosilicon, manganese
Iron, calcium carbide, silico-calcium, magnesium, aluminium or rare earth metal.
3. method according to claim 1 or 2, which is characterized in that alkali in the step 1) leaching tungsten slag and reducing agent
Mass ratio is 3~30:1.
4. the method according to claim 1, wherein the temperature that restores of the pre-burning of the step 1) be 500~
1200 DEG C, the time of the pre-burning reduction is 0.1~3h.
5. the method according to claim 1, wherein in the step 2) slag former include calcium oxide, aluminium oxide,
One or more of calcium hydroxide and dolomite.
6. method according to claim 1 or 5, which is characterized in that the quality of primary slag and slag former in the step 2)
Than for 3~50:1.
7. the method according to claim 1, wherein in the step 2) smelting reduction temperature be 1400~
1600 DEG C, the time of smelting reduction is 0.5~5h.
8. the method according to claim 1, wherein the content of As, Pb and Hg are only in the secondary slag of the step 2)
On the spot it is lower than 100ppm.
9. the method according to claim 1, wherein ferroalloy is by following mass percentage in the step 2)
Element composition: the total content 1~5% of manganese 5~30%, tungsten and niobium, remaining is iron.
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| CN110066146A (en) * | 2019-04-23 | 2019-07-30 | 南昌大学 | The recycling of tungsten slag and reuse method |
| CN110016563B (en) * | 2019-04-24 | 2020-11-06 | 江西理工大学 | High-value utilization method of high-temperature carbon reduction black tungsten slag |
| CN109881016B (en) * | 2019-04-24 | 2021-07-09 | 江西理工大学 | Method for harmless treatment of alkali-boiled tungsten residues and extraction of valuable metals |
| CN111057855B (en) * | 2019-12-24 | 2022-02-18 | 南昌大学 | Tungsten smelting slag alloying and microcrystallization synchronous treatment method |
| CN111440953B (en) * | 2020-05-25 | 2021-10-08 | 赣州有色冶金研究所有限公司 | Method for synergistically recycling tungsten slag and multi-element iron-rich slag |
| CN111826529B (en) * | 2020-06-28 | 2021-10-22 | 河南豫光金铅股份有限公司 | Separation smelting method of high-arsenic high-lead copper alloy |
| CN113999978B (en) * | 2021-11-04 | 2023-06-30 | 江西钨业控股集团有限公司 | Method for recovering valuable metals from tungsten slag |
| CN114524553A (en) * | 2022-03-16 | 2022-05-24 | 赣州八0一钨业有限公司 | Process for treating heavy metal wastewater by using alkaline-boiling tungsten slag |
| CN116693272B (en) * | 2023-08-10 | 2023-11-03 | 北京建工环境修复股份有限公司 | Tungsten slag recycling method and tungsten slag curing material |
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| CN102108449A (en) * | 2009-12-29 | 2011-06-29 | 厦门紫金矿冶技术有限公司 | Method for preprocessing scheelite and preparing ferro-tungsten |
| CN105586491A (en) * | 2016-01-18 | 2016-05-18 | 重庆科技学院 | Comprehensive recycling method for waste hard alloy |
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