CN107326400B - A kind of the low temperature molten salt electrolysis clean metallurgical method and device of antimony - Google Patents
A kind of the low temperature molten salt electrolysis clean metallurgical method and device of antimony Download PDFInfo
- Publication number
- CN107326400B CN107326400B CN201710775124.0A CN201710775124A CN107326400B CN 107326400 B CN107326400 B CN 107326400B CN 201710775124 A CN201710775124 A CN 201710775124A CN 107326400 B CN107326400 B CN 107326400B
- Authority
- CN
- China
- Prior art keywords
- antimony
- low temperature
- molten salt
- temperature molten
- fused salt
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Antimong-containing material, inertia fused salt are mixed and are placed in low temperature molten salt electrolysis device by certain distributing mode, low temperature molten salt electrolysis melting is carried out under the conditions of certain temperature and pulse current by a kind of the low temperature molten salt electrolysis clean metallurgical method and device of antimony.With the progress of low temperature molten salt electrolysis, fused salt mixt gradually forms " three layers of melt " structure in burner hearth.Antimong-containing material can be continuously added to from antimong-containing material feed opening, and obtained liquid antimony can put the releasing of antimony mouth from lower part.Existing antimony concentrate pyrogenic attack temperature is greatly reduced in the present invention, and a step output high-grade antimony has the advantages that low energy consumption, antimony direct yield is high, clean and environmental protection compared with existing antimony concentrate pyrometallurgical smelting process.The device of the invention is simple and practical, matches the antimony Extraction metallurgy effect that can have been obtained.
Description
Technical field
The present invention relates to clean metallurgical methods and device that a kind of antimong-containing material low temperature molten salt electrolysis obtains star metal, belong to coloured
Metal metallurgy smelting field.
Background technique
Antimony (Sb) is a kind of silvery white brittle metal, is a kind of acid-proof substances at normal temperature.It is a kind of widely used
Metal is known as " fire extinguishing fireproof person who has rendered outstanding service ", " strategy metal ", " metallic hard agent ", " protective agent of fluorescent tube, electron tube ".
The existing production method of metallic antimony, can be divided into pyrogenic process and wet process two major classes." blast furnace volatile smelting-reverberatory furnace is also
Former melting " is current most important antimony pyrometallurgical smelting technique, and the technique is first by stibnite concentrate or antimong-containing material through briquetting or granulation
Afterwards, blast furnace is added together with coke and flux, is carried out under the operation system of " low column, the thin bed of material, high coke yield, hot-top "
Volatile smelting makes antimony trisulfide volatilization oxidation, to separate with gangue and other impurity, the antimony oxide of generation enters together with flue gas
It condenses dust collecting system to collect, then through reduction smelting in reverberatory furnace output needle antimony.This technique is strong to adaptability to raw material, and processing capacity is big,
But the defects of generally existing coke rate is high, energy consumption is high, dust collecting system is huge, trivial operations.Especially in blast furnace volatile smelting work
Sequence generates low concentration SO2Flue gas and heavy metal dusts, serious pollution of ecological environment are that a still unsolved technology is difficult so far
Topic.
And also there is also many problems for method for existing antimony hydrometallurgy：1) vulcanized sodium leaching-thioantimonious acid sodium solution electricity
In area method, sodium sulphate, sodium thiosulfate, sodium sulfite and schlippe's salt accumulation are serious；Liquid waste processing amount is big and more many and diverse；Electricity
Low efficiency is flowed, power consumption is high.2) hydrogen reduction method of Sodium thioantimonite leachate is technically feasible, but the method has reduction
Speed is slow, antimony powder bonding reaction tube wall, blocks the problems such as pipeline.3)FeCl3In leaching-electrodeposition method, solution impurity accumulating rate
Comparatively fast；Anion-exchange membrane is more expensive and loss is very fast, and electrodeposition control condition is harsh；As, Au separation are difficult in leached mud；It is raw
It is still higher than pyrogenic process to produce cost.4) chlorination-Hydrolyze method technique requires a large amount of water dilute solution, and acid consumption is high, water consume is big, reagent consumption
Amount is big, and the production cycle is long, and wastewater discharge is big.5) slurry electrolysis is theoretically more feasible, but in practical electrolysis production mistake
The problems such as serious there are the loss of the dispersion of valuable element, the accumulation of harmful element, pole plate and diaphragm bag in journey, affect electrolysis
It operates normally, there are also to be verified for engineering application prospect.
In addition, in the production of China's non-ferrous metal, the low concentration sulphur dioxide flue gas one of sulphide ore smelting process generation
It is directly one of the important sources of China's acid rain, with the progress of production technology, the sulphide ores such as copper, lead, tin, cobalt, nickel are using oxygen-enriched
Intensified smelting technology can solve substantially low-concentration sulfur dioxide pollution problem to solve this problem, and in recent years, many researchers taste
Oxygen enriched molten bath melting technique that examination will be succeeded in smelting industries such as copper, lead, tin (such as bottom blowing, top blast, side-blown) is answered
For the smelting of stibnite concentrate, to solve antimony smelting process low concentration SO2The problems such as pollution.But it from theory analysis and opens
From the point of view of the experimental results of exhibition, oxygen-enriched intensified smelting technology is also difficult to the smelting applied to antimony at present.It is rich for antimony smelting
Oxygen intensified smelting and SO2There are a contradiction, contradictory core is the volatile decomposition of antimony trisulfide high temperature itself for relieving haperacidity.This is sulphur
Change the characteristic of antimony inherently.Simultaneously as the outermost 5S of Sb electron configuration2p3Structure, so that Sb is in intensified smelting difference oxygen
There are a variety of valence states under gesture, lead to the straight nozzle of oxygen Sb easy to form2O4、SbXOYAnd it is other be easy to dross object phase, when serious
Burner hearth, flue, etc. will be blocked.So that oxygen enriched molten bath or flash smelting technology are dfficult to apply to the smelting of antimony.In addition, because its
The reasons such as production scale is relatively small, and treating capacity is difficult to scale up cause the antimony in China to be smelted at present mostly also using traditional " drum
The production of wind furnace volatilization+reverberatory furnace high temperature reduction melting " technique.The sulfur dioxide concentration that smelting process generates is unable to reach relieving haperacidity and wants
It asks, can only directly empty, not only pollute surrounding enviroment, the sulphur in antimony concentrate also fails to realize that resource utilization utilizes.It is comprehensive next
It sees, still there is also common problems such as " low efficiency, energy consumption height, secondary pollution weight " for the existing antimony smelting process in China.It is filled from antimony resource
Recycling and environmental protection angle is divided to consider meter, low-carbon, the technical meaning of cleaning smelting for developing a kind of antimony are great.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that star metal is made in new slave antimong-containing material, reduce antimony and smelt temperature
Degree mitigates smelting process heavy metal to environment to improve the problems such as energy consumption present in current antimony smelting process is high, the device is complicated
Pollution, a step produces high-grade star metal, improves antimony direct yield, while recycling the Sulphur ressource of association in antimony concentrate.Realize antimony
Clean manufacturing reaches energy-saving and emission-reduction, the value-added purpose of consumption reduction.
Another object of the present invention is to provide a kind of matched with above-mentioned antimong-containing material molten-salt electrolysis metallurgical method, simply
It is practical, a kind of smelting device of the antimony metallurgical effect obtained can be integrated.
The technical scheme is that：
A kind of low temperature molten salt electrolysis clean metallurgical method of antimony, antimong-containing material is mixed with a part of inertia fused salt be placed in it is low
In temperature molten salt electrolysis unit, then remaining inertia fused salt is laid in the upper layer of the mixture, in certain temperature and pulse
Low temperature molten salt electrolysis melting is carried out under current condition；With the progress of low temperature molten salt electrolysis, it is molten to obtain liquid antimony for lower layer in device
Body layer.
The inertia fused salt is the mixture of sodium chloride, potassium chloride, the combination fused salt with vulcanized sodium or potassium sulfide, chlorination
In sodium, potassium chloride mixture, the ratio of the amount of sodium chloride and potassium chloride substance is 0.5~2:1, i.e. molNaCl:molKCl=0.5~
2:1, combining the mass percentage of vulcanized sodium or potassium sulfide in fused salt is 1wt.%~30wt.%.
The mass values of the method, antimong-containing material and inertia fused salt are 0.1~1:1.
The method, antimong-containing material is mixed with inertia fused salt and distributing mode is preferably：First by antimong-containing material with
30%~70% inertia fused salt is laid in low temperature molten salt electrolysis bottom of device after mixing, later by remaining inertia fused salt
It is laid in the upper layer of the mixture.This distributing mode is more advantageous to fused salt mixt in device and forms " three layers of melt " structure, has
Conducive to the progress of Molten.
With the progress of low temperature molten salt electrolysis, the fused salt mixt in device gradually forms " three layers of melt " structure.Upper layer is
Inertia molten salt layer, centre are antimong-containing material layer, and lower layer is liquid antimony layer.
The method, molten-salt electrolysis temperature are 800 DEG C~1000 DEG C.
The method, the pulse frequency of impulse electric field are 50~2000Hz, and duty ratio is 50%~90%, and electrolysis is initial
Average pulse current density is set as 50~500A/m2, tank voltage controls within 2.3V, and anode and cathode is away from for 2~10cm.
The method, antimong-containing material are more high-grade stibnite concentrate or antimony oxide material or high antimony content
The earth of positive pole, antimony content are all larger than 30wt.%.
A kind of device of the low temperature molten salt electrolysis clean metallurgical of antimony, including enclosed burner hearth, cathode collector bar, anode are led
Bar, graphite anode and the pulse power；Using graphite as liner, burner hearth bottom is equipped with for discharging for the side wall of the burner hearth and bottom
Put antimony mouth, top is equipped with exhanst gas outlet, and side wall upper part is equipped with inertia fused salt feed opening, is equipped with antimong-containing material in the middle part of side wall and feeds
Mouthful, lower sidewall is equipped with slag tap；One end of cathode collector bar is connected with the graphite liner of burner hearth bottom, the other end by conducting wire with
Pulse power cathode is connected, and one end of anode rod is protruded into from roof of the furnace, is connected with graphite anode, the other end by conducting wire and
The anode of the pulse power is connected.
The material of the device, cathode collector bar and anode rod is stainless steel or refined copper.
The device, burner hearth are provided with resistance heating layer outside graphite liner, and exhanst gas outlet receives dirt cloth bag.
In conclusion the present invention is designed by specific cryogenic inert molten salt system, it is allowed to the model at 800 DEG C~1000 DEG C
The interior low-temperature molten salt for forming good fluidity is enclosed, provides stable reaction media for the melten salt electriochemistry reduction of antimony concentrate.Meanwhile
Na in fused salt2S or K2The introducing of S is the reduction of antimony and S in antimony concentrate2-Oxidation provide electron transfer pathways, may be implemented
One step of antimony concentrate low temperature molten salt electrolysis obtains the purpose of antimony and elemental sulfur.In addition, the present invention carries out fused salt electricity using pulse current
Solution controls under specific electric current and voltage, enables the antimony selective reduction in antimony concentrate, impurity element or remains in antimony smelting
It refines in slag or enters in fused salt, realize efficiently separating for antimony in antimony concentrate.
Compared with existing antimony smelting blast furnace volatilization-reverberatory furnace high temperature pyrogenic process reducing and smelting technique, the present invention can substantially drop
Low antimony concentrate pyrometallurgical smelting temperature, a step output high-grade antimony simultaneously recycle elemental sulfur, with process is short, low energy consumption, antimony direct yield
High advantage.It can reduce pollution of the antimony concentrate smelting process harmful heavy metal to surrounding enviroment, to promotion China's antimony metallurgical technology
Progressive and energy-saving and emission-reduction are of great significance.
Detailed description of the invention
Fig. 1 is low temperature molten salt electrolysis schematic device of the invention.
1- anode rod in figure, 2- graphite anode, the 3- pulse power, 4- inertia fused salt feed opening, the charging of 5- antimong-containing material
Mouthful, 6- puts antimony mouth, 7- exhanst gas outlet, 8- cathode collector bar, 9- graphite liner, 10- resistance heating layer, 11- slag tap, 12- burner hearth,
13- inertia molten salt layer, 14- antimong-containing material layer, 15- liquid antimony layer.
Specific embodiment
Following embodiment is intended to further illustrate the present invention, without will form limitation of the invention.
Low temperature molten salt electrolysis device of the present invention, including enclosed burner hearth [12], cathode collector bar [8], anode rod [1],
Graphite anode [2] and the pulse power [3]；The side wall of the burner hearth [12] and bottom are using graphite as liner, burner hearth [12] bottom
Equipped with putting antimony mouth [6] for discharging, top is equipped with exhanst gas outlet [7], and side wall upper part is equipped with inertia fused salt feed opening [4], side
Antimong-containing material feed opening [5] are equipped in the middle part of wall, lower sidewall is equipped with slag tap [11]；One end of cathode collector bar [8] and burner hearth
[12] graphite liner [9] of bottom is connected, and the other end is connected by conducting wire with the pulse power [3] cathode, and the one of anode rod [1]
End is protruded at the top of burner hearth [12], is connected with graphite anode [2], and the other end is connected by conducting wire with the anode of the pulse power [3].
Burner hearth [12] is provided with resistance heating layer [10] outside graphite liner, and exhanst gas outlet receives dirt cloth bag.
Embodiment 1
The chemical composition of antimony concentrate A is (%)：Sb 54.7,Fe 2.8,S 15.7,As 0.35,Pb 0.22,SiO2
11.4,Au 87.5g/t.100g antimony concentrate A, 20g Na are weighed respectively2The KCl of S, 79.1g NaCl and 100.9g.First will
20g Na2The KCl of S, 79.1g NaCl and 100.9g are uniformly mixed.The fused salt mixt and 100g antimony concentrate A of 80g are taken out later
It continuess to mix uniformly.The mixed material is laid in low temperature molten salt electrolysis device burner hearth bottom by antimong-containing material feed opening
Remaining 120g fused salt mixt is laid in the upper layer of mixture by portion by inertia fused salt feed opening later.Adjust anode rod
Height, be inserted into graphite anode in the inertia fused salt on upper layer, and make anode and cathode pole span 4cm.Open non-essential resistance heating
Layer power supply, is warming up to 880 DEG C.The pulse power is opened, setting inceptive impulse average current density is 300A/m2, control flume is pressed in
Between 1.8~2.1V.After reacting 4h, reaction was completed.It puts antimony mouth and is collected into antimony 51.2g, antimony grade 98.8%, antimony direct yield
92.5%, the simple substance S 8.9g that purity is 94.2% is collected into fume collection cloth bag.
Embodiment 2
The chemical composition of antimony concentrate B is (%)：Sb 32.6,Fe 16.9,S 32.4,As 1.3,SiO2 13.7、Pb
0.17,Au 77.5g/t.200g antimony concentrate B, 100g K are weighed respectively2The KCl of S, 175.8g NaCl and 224.2g.First will
100g K2The KCl of S, 175.8g NaCl and 224.2g are uniformly mixed.Later from the uniformly mixed fused salt take out 160g with
200g antimony concentrate B is uniformly mixed.The mixed material is laid in low temperature molten salt electrolysis device by antimong-containing material feed opening
The tiling of remaining 240g fused salt mixt is passed through inertia fused salt feed opening on the upper layer of mixture later by burner hearth bottom.Adjustment sun
The height of pole guide rod is inserted into graphite anode in the inertia fused salt on upper layer, and makes anode and cathode pole span 8cm.Open external electrical
Heating layer power supply is hindered, is warming up to 920 DEG C.The pulse power is opened, setting inceptive impulse average current density is 350A/m2, control
Slot is pressed between 1.7~2.0V.After reacting 4h, reaction was completed.It puts antimony mouth and is collected into antimony 64.2g, antimony grade 96.6%, antimony is directly received
Rate 95.1% is collected into the simple substance S 17.9g that purity is 92.4% in fume collection cloth bag.
Embodiment 3
The chemical composition of antimony concentrate C is (%)：Sb 78.2,As 2.6,Fe 1.6,Pb 0.3.100g antimony essence is weighed respectively
Mine C, 15g Na2The KCl of S, 48.3g NaCl and 61.7g.First by 15g Na2The KCl of S, 48.3g NaCl and 61.7g are mixed
Uniformly.50g is taken out from the uniformly mixed fused salt later to be uniformly mixed with 100g antimony concentrate C.The mixed material is led to
It crosses antimong-containing material feed opening and is laid in low temperature molten salt electrolysis device burner hearth bottom, remaining 75g fused salt mixt tiles later logical
Inertia fused salt feed opening is crossed on the upper layer of mixture.The height for adjusting anode rod, makes graphite anode be inserted into the inertia on upper layer
In fused salt, and make anode and cathode pole span 6cm.Non-essential resistance heating layer power supply is opened, is warming up to 850 DEG C.The pulse power is opened, if
Setting inceptive impulse average current density is 250A/m2, control flume is pressed between 1.5~1.8V.After reacting 3.5h, reaction was completed.
It puts antimony mouth and is collected into antimony 77.9g, antimony grade 98.1%, antimony direct yield 97.7%.After the test in fume collection cloth bag not
It is collected into elemental sulfur.
Embodiment 4
Antimony concentrate low temperature molten salt electrolysis is carried out with raw material same in above-described embodiment 2 and test parameters, after reacting 4h, from
It puts after antimony mouth releases antimony 35g and stops putting antimony.Later, antimony concentrate B100g is added into molten salt system from antimong-containing material feed opening, protects
It is constant to hold each test parameters, continues to react.After reacting 3.5h, reaction was completed, will put antimony that antimony mouth is collected into and puts before
35g antimony out merges weighing, analyzes its grade.The result shows that molten-salt electrolysis twice is collected into antimony 94.8g, antimony grade altogether
97.5%, antimony direct yield 94.5%.The simple substance S 17.3g that purity is 93.9% is collected into fume collection cloth bag.
Comparative example 1 (non-pulse current electroanalysis)
Carried out with raw material described in above-described embodiment 1 and is tested.100g antimony concentrate A, 20g Na are weighed respectively2S, 79.1g
The KCl of NaCl and 100.9g.First by 20g Na2The KCl of S, 79.1g NaCl and 100.9g are uniformly mixed.Later from the mixing
80g is taken out in uniform fused salt to be uniformly mixed with 100g antimony concentrate A.The mixed material is laid in low temperature molten salt electrolysis dress
Burner hearth bottom is set, remaining 120g fused salt mixt is laid in the upper layer of mixture later.The height for adjusting anode rod, makes stone
Black anode is inserted into the inertia fused salt on upper layer, and makes anode and cathode pole span 4cm.Open non-essential resistance heating layer power supply, heating
To 880 DEG C.Molten-salt electrolysis is carried out using common power, setting initial current density is 300A/m2, control flume is pressed in 1.8~
Between 2.1V.After reacting 4h, reaction was completed.It is collected into antimony 32.3g, antimony grade 89.2%, antimony direct yield 52.7% is received in flue gas
The simple substance S 4.3g that purity is 88.4% is collected into collection cloth bag.
Comparative example 2 (is not added with Na2S or K2S)
Carried out with raw material described in above-described embodiment 1 and is tested.Weigh respectively 100g antimony concentrate A, 87.9g NaCl and
The KCl of 112.1g.The KCl of 87.9g NaCl and 112.1g are uniformly mixed first.It is taken from the uniformly mixed fused salt later
80g is uniformly mixed with 100g antimony concentrate A out.The mixed material is laid in low temperature molten salt electrolysis device burner hearth bottom, it
Remaining 120g fused salt mixt is laid in the upper layer of mixture afterwards.The height for adjusting anode rod, is inserted into graphite anode
In the inertia fused salt on upper layer, and make anode and cathode pole span 4cm.Non-essential resistance heating layer power supply is opened, is warming up to 880 DEG C.It is open-minded
The pulse power, setting inceptive impulse average current density are 300A/m2, control flume is pressed between 1.8~2.1V.After reacting 4h,
Reaction was completed.It is collected into antimony 41.1g, antimony grade 82.3%, antimony direct yield 61.8% is only collected into fume collection cloth bag and contains
Sulphur flue dust 0.9g, sulfur content 87.1%.
Comparative example 3 (unspecific temperature)
Carried out with raw material described in above-described embodiment 2 and is tested.200g antimony concentrate B, 100g K are weighed respectively2S, 175.8g
The KCl of NaCl and 224.2g.First by 100g K2The KCl of S, 175.8g NaCl and 224.2g are uniformly mixed.It is mixed from this later
Taking-up 160g in uniform fused salt is closed to be uniformly mixed with 200g antimony concentrate B.The mixed material is laid in low-temperature molten salt electricity
Device burner hearth bottom is solved, remaining 240g fused salt mixt is laid in the upper layer of mixture later.The height of anode rod is adjusted,
It is inserted into graphite anode in the inertia fused salt on upper layer, and makes anode and cathode pole span 8cm.Non-essential resistance heating power supply is opened, is risen
Temperature is to 700 DEG C.The pulse power is opened, setting inceptive impulse average current density is 350A/m2, control flume is pressed in 1.7~2.0V
Between.After reacting 4h, reaction was completed.It is only collected into antimony 7.2g, antimony grade 85.1%, a large amount of antimony concentrate is also unfused, not
Reaction is participated in, antimony direct yield only 9.4% is not collected into sulphur in fume collection cloth bag.
Comparative example 4 (unspecific slot pressure)
Carried out with raw material described in above-described embodiment 3 and is tested.100g antimony concentrate C, 15g Na are weighed respectively2S, 48.3g
The KCl of NaCl and 61.7g.First by 15g Na2The KCl of S, 48.3g NaCl and 61.7g are uniformly mixed.It is equal from the mixing later
50g is taken out in even fused salt to be uniformly mixed with 100g antimony concentrate C.The mixed material is laid in low temperature molten salt electrolysis device
Remaining 75g fused salt mixt is laid in the upper layer of mixture by burner hearth bottom later.The height for adjusting anode rod, makes graphite
Anode is inserted into the inertia fused salt on upper layer, and makes anode and cathode pole span 6cm.Non-essential resistance heating power supply is opened, is warming up to 850
℃.The pulse power is opened, setting inceptive impulse average current density is 250A/m2, control flume pressure is greater than 3.0V.React 3.5h
Afterwards, reaction was completed.It is collected into needle antimony 76.3g, antimony grade 89.2% contains arsenic 2.1%, and leaded 0.5%, antimony direct yield 87%.
Comparative example 5 (unspecific distributing mode)
Carried out with raw material described in above-described embodiment 1 and is tested.100g antimony concentrate A, 20g Na are weighed respectively2S, 79.1g
The KCl of NaCl and 100.9g.Later by 100g antimony concentrate A, 20g Na2The KCl of S, 79.1g NaCl and 100.9g are uniformly mixed.
The mixed material is laid in low temperature molten salt electrolysis device burner hearth bottom by antimong-containing material feed opening.Adjust anode rod
Height, be inserted into graphite anode in mixed material, and make anode and cathode pole span 4cm.Non-essential resistance heating layer power supply is opened,
It is warming up to 880 DEG C.The pulse power is opened, setting inceptive impulse average current density is 300A/m2, control flume is pressed in 1.8~
Between 2.1V.After reacting 4h, reaction was completed.It puts antimony mouth and is collected into antimony 30.3g, antimony grade 79.3%, antimony direct yield 43.9%,
The simple substance S 2.1g that purity is 90.2% is collected into fume collection cloth bag.
Claims (5)
1. a kind of low temperature molten salt electrolysis clean metallurgical method of antimony, which is characterized in that by antimong-containing material and a part of inertia fused salt
Mixing be placed in low temperature molten salt electrolysis device, then remaining inertia fused salt is laid in the upper layer of the mixture, 800 DEG C ~
Low temperature molten salt electrolysis melting is carried out under the conditions of 1000 DEG C and pulse current；With the progress of low temperature molten salt electrolysis, lower layer in device
Obtain liquid antimony melt layer；The inertia fused salt is the mixture of sodium chloride, potassium chloride, and the combination with vulcanized sodium or potassium sulfide is molten
Salt, in sodium chloride, potassium chloride mixture, the ratio of the amount of sodium chloride and potassium chloride substance is 0.5 ~ 2:1, combine vulcanized sodium in fused salt
Or the mass percentage of potassium sulfide is the wt.% of 1 wt.% ~ 30.
2. the method according to claim 1, wherein the mass values of antimong-containing material and inertia fused salt are 0.1 ~ 1:
1。
3. method according to claim 1 or 2, which is characterized in that first by the inertia of antimong-containing material and the % of 30 % ~ 70
Fused salt is laid in low temperature molten salt electrolysis bottom of device after mixing, and remaining inertia fused salt is laid in the mixture later
Upper layer.
4. the method according to claim 1, wherein the pulse frequency of impulse electric field is 50 ~ 2000 Hz, duty
Than being 50% ~ 90%, electrolysis inceptive impulse average current density is set as 50 ~ 500 A/m2, tank voltage control within 2.3 V,
Anode and cathode is away from for 2 ~ 10 cm.
5. the method according to claim 1, wherein antimong-containing material is more high-grade stibnite concentrate or oxidation
The earth of positive pole of antimony material or high antimony content, antimony content are all larger than 30 wt.%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710775124.0A CN107326400B (en) | 2017-08-31 | 2017-08-31 | A kind of the low temperature molten salt electrolysis clean metallurgical method and device of antimony |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710775124.0A CN107326400B (en) | 2017-08-31 | 2017-08-31 | A kind of the low temperature molten salt electrolysis clean metallurgical method and device of antimony |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107326400A CN107326400A (en) | 2017-11-07 |
| CN107326400B true CN107326400B (en) | 2018-11-30 |
Family
ID=60204812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710775124.0A Active CN107326400B (en) | 2017-08-31 | 2017-08-31 | A kind of the low temperature molten salt electrolysis clean metallurgical method and device of antimony |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107326400B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110863218B (en) * | 2019-11-27 | 2021-11-30 | 东北大学 | Method for extracting gold by adopting molten salt electrolysis enrichment |
| CN111172563B (en) * | 2020-02-25 | 2020-12-29 | 中南大学 | Method and device for electrolyzing antimony sulfide-containing material by using molten salt |
| CN115012003B (en) * | 2022-06-20 | 2024-02-06 | 中南大学 | Method and device for continuously producing antimony sulfide ore through molten salt electrolysis |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103898553B (en) * | 2014-03-25 | 2016-06-22 | 中国科学院过程工程研究所 | A kind of electrodeposition and refine are synchronously performed the method producing calcium metal |
| CN104313643A (en) * | 2014-07-31 | 2015-01-28 | 贵州重力科技环保有限公司 | High-purity antimony producing method by two-section fused salt electrolysis method |
| CN204265863U (en) * | 2014-11-25 | 2015-04-15 | 北京有色金属研究总院 | A kind of carbon vessel for fused salt electrolysis |
| CN104477965B (en) * | 2014-12-15 | 2016-03-30 | 武汉大学 | The method of a kind of gas/fused salt surface reaction synthetic metals sulfide |
| CN104746105B (en) * | 2015-04-14 | 2017-06-06 | 锡矿山闪星锑业有限责任公司 | It is a kind of to separate the device and method containing antimony alloy |
-
2017
- 2017-08-31 CN CN201710775124.0A patent/CN107326400B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107326400A (en) | 2017-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101935766B (en) | Method and device for smelting jamesonite by bottom-blowing pool | |
| CN1311090C (en) | Bessemer matte production method using nickel sulfide materials | |
| CN101649396B (en) | Methods of removing F and Cl in secondary zinc oxide dust effectively and producing electrolytic zinc | |
| CN107326400B (en) | A kind of the low temperature molten salt electrolysis clean metallurgical method and device of antimony | |
| CN104498731B (en) | A kind of method and apparatus of the solid sulfur melting of oxygen-enriched side-blowing low-temperature alkali | |
| CN102433448A (en) | Smelting method of antimony-zinc-lead-containing concentrate | |
| CN105349791B (en) | A kind of method of selective extraction copper in copper matte regulus material from iron | |
| CN105624412B (en) | A kind of method that Combined Treatment is selected in Bellamya aeruginosa smelting | |
| CN103388081A (en) | Bath smelting method and apparatus of zinc sulfide concentrate and lead-zinc containing materials | |
| CN105950869B (en) | A kind of method for improving zinc hydrometallurgy lead smelting gas high-efficiency resource recycling collocation amount | |
| CN103382527A (en) | Flash smelting method and device for zinc sulfide concentrates and materials containing lead and zinc | |
| CN108913898A (en) | A kind for the treatment of process of high bismuth lead anode slurry | |
| CN103343174A (en) | Method for separating titanium, iron, vanadium and calcium from mixed titaniferous slag | |
| CN110004298A (en) | A kind of industry dangerous waste Resource comprehensive utilization method | |
| CN106011497B (en) | A kind of method that lead bullion is reclaimed from lead copper matte | |
| CN106086413B (en) | A kind of technique of zinc hydrometallurgy lead smelting gas recycling | |
| CN105695744A (en) | Full-path full-valence separation method for multifarious metal | |
| CN101871725A (en) | Horizontal bottom blowing type molten pool desulphurizing furnace and oxidative desulphurization method for leaded materials | |
| CN106591592A (en) | Rich metallurgy smelting furnace and treatment process for treating polymetallic complex auricupride | |
| CN107447107B (en) | A kind of method that wealth and rank antimony control current potential is separated and recovered from base metal | |
| CN108624759A (en) | A method of the comprehensively recovering valuable metal from white cigarette dirt | |
| CN106591600A (en) | Method for preparing high-titanium slag through low-temperature gas-based reduction titanium-containing iron mineral powder | |
| CN111172563B (en) | Method and device for electrolyzing antimony sulfide-containing material by using molten salt | |
| CN103374658A (en) | Ultrafine lead oxide prepared from desulfurated lead plaster by means of three-stage process and method thereof | |
| CN106148736B (en) | The device and method of iron, slag and rare-earth phase in cryogenic separation Rare Earth Mine reduced ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |