CN107312940B - A kind of method that mercury antimony is extracted in the collaboration of mercury antimony composite ore - Google Patents
A kind of method that mercury antimony is extracted in the collaboration of mercury antimony composite ore Download PDFInfo
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- CN107312940B CN107312940B CN201710315524.3A CN201710315524A CN107312940B CN 107312940 B CN107312940 B CN 107312940B CN 201710315524 A CN201710315524 A CN 201710315524A CN 107312940 B CN107312940 B CN 107312940B
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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
- C22B30/02—Obtaining antimony
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/24—Alloys obtained by cathodic reduction of all their ions
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Abstract
A kind of method that mercury antimony is extracted in the collaboration of mercury antimony composite ore, is related to the absorption of mercury.The method that mercury antimony is extracted in mercury antimony composite ore collaboration, acquisition mercury antimony rich solution after once being leached, being once separated by solid-liquid separation, mercury antimony rich solution is obtaining mercury antimony alloy after electro-deposition twice, mercury antimony alloy obtains thick mercury and needle antimony after vacuum separation, smart mercury is obtained after the purification of thick mercury, obtains No. 1 antimony after coarse antimony refining.This method has easy to operate, overall process clean and environmental protection, the high feature of the rate of recovery of mercury metal and metallic antimony, wherein the comprehensive recovery of mercury metal is greater than 99%, and the comprehensive recovery of metallic antimony is greater than 97%.
Description
Technical field
The present invention relates to the absorption of mercury, in particular to a kind of method that mercury antimony is extracted in the collaboration of mercury antimony composite ore.
Background technique
The main beneficiating method of mercury antimony ore metallurgical method, the vacuum distillation method of mercury antimony concentrate, wet process and combination method etc.；Beneficiating method is excellent
Floatation is first used, flotation sub-elects mercury concentrate, antimony concentrate, and separation process present in mercury antimony floatation separation process is complicated, floats
Choosing can generate new pollution using infectious agent, and processing cost is high, and the product isolated mutually contains that rate is high and the rate of recovery is low equal scarce
Point；
Vacuum distillation method has advantage compared with roasting oxidation smelting process, but there is also distillation treating tail gas difficulty, environmental protection facilities
It is huge, the disadvantages of operating cost is high；There are two types of technologies for combination method, and one is antimony hydrometallurgy-pyrogenic processes to refine mercury, and one is pyrogenic process steamings
Mercury, antimony hydrometallurgy, both techniques have environment-friendly advantage, but complex process compared with vacuum distillation method, and equipment investment is big；Wet-treating
Mercury antimony ore has many advantages, such as that process is simple, and opposite process is short, represents the development trend of the following mercury antimony metallurgy.
Publication No. CN1035680A, the application for a patent for invention that patent name is " the Hg-Sb separation method of mercury antimony grandidierite "
In, a kind of use flotation-hydrometallurgy combination method separating hydrargyrum antimony process is disclosed, which can effectively realize Hg-Sb separation, but mercury
Separation process present in antimony floatation separation process is complicated, and flotation can generate new pollution, and processing cost using infectious agent
Height, the product isolated mutually contain the disadvantages such as rate is high and the rate of recovery is low；
In the application for a patent for invention that Publication No. CN101643860A, patent name are " using blast furnace oxidizing roasting ",
Separate mercury in the form of mercury vapour with antimony oxide, mercury vapour condensing recovery, antimony oxide restores again smelting production
Metallic antimony；As adding for discharge standard is tight, the technical process is seriously polluted, and environment protection treating is extremely difficult, it is difficult to row up to standard
It puts.
Publication No. CN102851505A, patent name are the hair of " method of antimony mercury is separated from shahovite flue gas during smelting "
In bright patent application, pyrolytic semlting method is also used, but it pollutes weight in smelting process, treatment cost is high, and is difficult to
Qualified discharge.
Summary of the invention
Mercury antimony is extracted in view of the deficienciess of the prior art, cooperateing with the object of the present invention is to provide a kind of mercury antimony composite ore
Method solves in the prior art the low disadvantage of the product recovery rate that environmental pollution is serious, isolates.
The technical scheme adopted by the invention is that: a kind of method that mercury antimony is extracted in the collaboration of mercury antimony composite ore, technical points
It is to include the following steps:
1) mercury antimony composite ore is crushed to 80 mesh after ore grinding and carries out once hereinafter, primary alkali leachate is then added
It leaches；Wherein primary alkali leachate contains Na2S 160~180g/L, NaOH 30~50g/L；Primary alkali leachate and broken
The mass ratio of mercury antimony composite ore afterwards is 3 ~ 5:1；Extraction time is 120 ~ 180min, and temperature is 20 DEG C ~ 35 DEG C；Obtain one
Secondary leaching material；
2) material filtering will be once leached, mercury antimony rich solution and a filter residue are obtained；Filtering uses full-automatic filters pressing mode；
3) mercury antimony rich solution carries out electro-deposition twice；When the electro-deposition of rich solution of mercury antimony, each constituent concentration of electrolytic solution are as follows: total
Mercury 85 ~ 100g/L, total 80 ~ 95g/L of antimony, Na220 ~ 30g/L of S120 ~ 140g/L, NaOH；180 ~ 240A/m of current density2, electrolysis
Liquid circulation rate are as follows: 20 ~ 30L/ slot point, solution temperature are 20 DEG C ~ 35 DEG C, electrolysis time electrolysis time for 24 hours ~ 30h；
Cathode plate is stainless steel plate or titanium alloy sheet, and anode is graphite plate or stainless steel plate；
When mercury antimony rich solution double electrodeposition, each constituent concentration of electrolytic solution are as follows: total mercury 2 ~ 4g/L, total 30 ~ 50g/L of antimony,
Na220 ~ 30g/L of S 140 ~ 180g/L, NaOH；150 ~ 160A/m of current density2, electrolyte circulation rate are as follows: 15 ~ 20L/ slot
Point, solution temperature is 50 DEG C ~ 60 DEG C, electrolysis time 2h ~ 3h, and cathode-anode plate is identical as an electro-deposition；Electro-deposition twice is completed
Mercury antimony alloy and mercury antimony lean solution are obtained afterwards；
4) mercury antimony alloy thermal release: using vacuum melting furnace, purges vacuum melting furnace air using nitrogen before thermal release,
It is subsequently placed into mercury antimony alloy, into the thermal release stage, heating uses 20 degree per minute, is heated to 500 ~ 550 DEG C of progress constant temperature, permanent
The h of warm 2.5h ~ 3, the steam condensation of generation enter water absorption tower and become thick mercury and needle antimony；
5) thick mercury purification, coarse antimony refining: thick mercury carries out impurity removal and purification using the concentrated sulfuric acid or concentrated hydrochloric acid and produces smart mercury；Needle antimony is adopted
Refining No. 1 antimony of production is carried out with pyrogenic process.
2, the method that mercury antimony is extracted in mercury antimony composite ore collaboration as described in claim 1, which is characterized in that mercury in step 1)
Leaching rate is greater than 96%, and leaching rate of antimony is greater than 93%.
In above-mentioned technical proposal, a filter residue is added secondary alkaline leaching liquid and carries out secondary leaching, secondary alkaline leaching liquid
Containing Na2S 120~140g/L, NaOH 20~30g/L；The mass ratio of secondary alkaline leaching liquid and a filter residue is 4 ~ 6:1；It leaches
Time is 90 ~ 120min, and extraction temperature is 50 DEG C ~ 75 DEG C, obtains secondary leaching material.
In above-mentioned technical proposal, by secondary leaching material filtering, secondary filtrate and secondary filter residue are obtained；Filtering uses entirely certainly
Mode is filtered in dynamic pressure；
Re-start the extraction of mercury antimony；
Secondary residue washing: secondary filter residue is through 30 DEG C ~ 40 DEG C water washings, and washing is using toward injection side in filter press frame
Formula, rear liquid to be washed can stop containing NaOH lower than 3g/L；The cleaning solution of acquisition returns to secondary alkaline leaching process；Wash residue warp
It stores up or comprehensively utilizes after filters pressing processing.
In above-mentioned technical proposal, in secondary alkaline leaching technique, the secondary leaching rate of mercury is greater than 98%, and the secondary leaching rate of antimony is big
In 96%.
In above-mentioned technical proposal, to step) vulcanized sodium crystallization is carried out by the mercury antimony lean solution that electro-deposition twice obtains in 3,
Mercury antimony lean solution crystallizes out vulcanized sodium by the way of water cooling, after centrifuge separation, obtains vulcanized sodium byproduct and mother liquor, mother liquor
Mixed liquor is leached with the primary alkali in step 1) to mix, and re-starts the extraction of mercury antimony.
The beneficial effects of the present invention are: the method that mercury antimony is extracted in mercury antimony composite ore collaboration, is once leached, a solid-liquid
Mercury antimony rich solution is obtained after separation, mercury antimony rich solution is obtaining mercury antimony alloy after electro-deposition twice, and mercury antimony alloy is through vacuum separation
After obtain thick mercury and needle antimony, smart mercury is obtained after the purification of thick mercury, obtains No. 1 antimony after coarse antimony refining.This method has operation letter
The high feature of the rate of recovery of list, overall process clean and environmental protection, mercury metal and metallic antimony, wherein the comprehensive recovery of mercury metal is greater than
99%, the comprehensive recovery of metallic antimony is greater than 97%.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Other attached drawings.
Fig. 1 is the method flow diagram that mercury antimony is extracted in the collaboration of mercury antimony composite ore in the embodiment of the present invention.
Specific embodiment
In the present embodiment, primary alkali is leached, during secondary alkaline leaching, and mixing speed is 120 ~ 140 revs/min；
Secondary filter residue is washed through warm water, and washing times are 3 ~ 6 times.
Embodiment 1:
Used in the present embodiment mercury antimony composite ore collaboration extract mercury antimony method, used mercury antimony composite ore it is main
Ingredient are as follows: Hg0.52%, Sb1.53%, specifically includes the following steps:
1) 80 wood are crushed to after ore grinding to mercury antimony composite ore, carry out primary alkali leaching；Primary alkali leachate is
The mixed liquor of Na2S and NaOH, 160g/L containing Na2S, NaOH 30g/L；It is 3 ~ 5:1 that leachate, which consolidates mass ratio,；When leaching
Between be 120min, extraction temperature be 20 DEG C, stirring frequency be 120 revs/min；Guarantee that leaching rate of mercury is greater than 96%, antimony once soaks
Extracting rate is greater than 93%；
2) primary to be separated by solid-liquid separation；Using full-automatic filters pressing mode, mercury antimony rich solution and a filter residue are isolated；Mercury antimony rich solution
Into electro-deposition process；One time filter residue enters secondary alkaline leaching；
Also carry out secondary alkaline leaching to a filter residue in the present embodiment: alkaline leaching liquid is the mixing of Na2S and NaOH
Liquid, 120g/L containing Na2S, NaOH 20g/L；It is 4:1 that secondary leachate, which consolidates mass ratio,；Extraction time is 90min, extraction temperature
It is 50 DEG C, stirring frequency is 120 revs/min；Guarantee that the secondary leaching rate of mercury is greater than 98%, the secondary leaching rate of antimony is greater than 96%；
The present embodiment also carries out secondary separation of solid and liquid, secondary separation of solid and liquid to by the alkaline leaching liquid of secondary alkaline leaching
Technical process are as follows: use full-automatic filters pressing mode, isolate secondary filtrate and secondary filter residue；Secondary filtrate and primary leaching work
Primary alkali in sequence leaches jointly after leaching mixed liquor mixing, re-starts the extraction of mercury antimony；Secondary filter residue is carried out simultaneously
Washing, secondary residue washing process are as follows: secondary filter residue is washed through warm water, using repeatedly, washing times are 3 times on a small quantity；Cleaning solution
It is leached jointly after being mixed with secondary leaching mixed liquor；Washing residue is stored up or is comprehensively utilized after filters pressing is handled；
3) mercury antimony rich solution electro-deposition twice；The condition of mercury antimony rich solution electro-deposition are as follows: electrolytic solution ingredient are as follows: total mercury
85g/L, total antimony 80g/L, Na2S 120g/L, NaOH 20g/L；Current density 180A/m2, electrolyte circulation rate are as follows: 20L/
Slot point, solution temperature are 20 DEG C, and electrolysis time 2h is electrolysed the reaction of generation are as follows:
Anode reaction formula are as follows: 4OH—-4e=H2O+O2,
Anode reaction formula are as follows: Sb3++3e=Sb,Hg2++2e=Hg；
Theoretical amount is precipitated as foundation using mercury in mercury antimony rich solution in electrolysis time, and cathode plate is stainless steel plate or titanium alloy sheet, sun
Extremely graphite plate or stainless steel plate；
Double electrodeposition condition are as follows: electrolytic solution ingredient are as follows: total mercury 2g/L, total antimony 30g/L, Na2S 140g/L, NaOH
20g/L；Current density 150A/m2, electrolyte circulation rate are as follows: 15L/ slot point, solution temperature are 50 DEG C DEG C；Cathode-anode plate with
Electro-deposition is identical；The mercury antimony alloy and mercury antimony lean solution that one double electrodeposition generates；Wherein, centrifugation point is carried out to mercury antimony lean solution
From vulcanized sodium crystallization is obtained, mercury antimony lean solution crystallizes out vulcanized sodium by the way of water cooling, mother liquor and primary alkali leachate, secondary
It leaches after leaching filtrate mixing, mercury antimony is extracted jointly again；
4) mercury antimony alloy thermal release；Thermal release is carried out to the mercury antimony alloy generated by a double electrodeposition, using vacuum
Smelting furnace purges furnace air using nitrogen before thermal release, is subsequently placed into mercury antimony alloy, into thermal release process, thermal release adds
Temperature uses 20 degree per minute, is heated to 500 DEG C of progress constant temperature, 2.5 h of constant temperature, and mercuryvapour condensation enters water absorption tower and becomes thick
Mercury, needle antimony enter coarse antimony refining process；
5) thick mercury purification, coarse antimony refining.Thick mercury carries out impurity removal and purification using the concentrated sulfuric acid or concentrated hydrochloric acid and produces smart mercury；Needle antimony is adopted
Refining No. 2 antimony of production are carried out with pyrogenic process.
This example mercury antimony comprehensive recovery is high, and mercury comprehensive recovery is greater than 99%, and antimony comprehensive recovery is greater than 98%.
Embodiment 2:
Used in the present embodiment mercury antimony composite ore collaboration extract mercury antimony method, used mercury antimony composite ore it is main
Ingredient are as follows: Hg0.52%, Sb1.53%, specifically includes the following steps:
1) 60 wood are crushed to after ore grinding to mercury antimony composite ore, carry out primary alkali leaching；Primary alkali leachate is
The mixed liquor of Na2S and NaOH, 170g/L containing Na2S, NaOH 40g/L；It is 4:1 that leachate, which consolidates mass ratio,；Extraction time
For 140min, extraction temperature is 25 DEG C, and stirring frequency is 130 revs/min；Guarantee that leaching rate of mercury is greater than 96%, antimony once leaches
Rate is greater than 93%；
2) primary to be separated by solid-liquid separation；Using full-automatic filters pressing mode, mercury antimony rich solution and a filter residue are isolated；Mercury antimony rich solution into
Enter electro-deposition process；One time filter residue enters secondary alkaline leaching；
Also carry out secondary alkaline leaching to a filter residue in the present embodiment: alkaline leaching liquid is the mixing of Na2S and NaOH
Liquid, 130g/L containing Na2S, NaOH 25g/L；It is 5:1 that secondary leachate, which consolidates mass ratio,；Extraction time is 100min, leaches temperature
Degree is 60 DEG C, and stirring frequency is 130 revs/min；Guarantee that the secondary leaching rate of mercury is greater than 98%, the secondary leaching rate of antimony is greater than 96%；
The present embodiment also carries out secondary separation of solid and liquid, secondary separation of solid and liquid to by the alkaline leaching liquid of secondary alkaline leaching
Technical process are as follows: use full-automatic filters pressing mode, isolate secondary filtrate and secondary filter residue；Secondary filtrate and primary leaching work
Primary alkali in sequence leaches jointly after leaching mixed liquor mixing, re-starts the extraction of mercury antimony；Secondary filter residue is carried out simultaneously
Washing, secondary residue washing process are as follows: secondary filter residue is washed through warm water, using repeatedly, washing times are 4 times on a small quantity；Cleaning solution
It is leached jointly after being mixed with secondary leaching mixed liquor；Washing residue is stored up or is comprehensively utilized after filters pressing is handled；
3) mercury antimony rich solution electro-deposition twice；The condition of mercury antimony rich solution electro-deposition are as follows: electrolytic solution ingredient are as follows: total mercury
90g/L, total antimony 90g/L, Na2S 130g/L, NaOH 25g/L；Current density 200A/m2, electrolyte circulation rate are as follows: 25L/
Slot point, solution temperature are 25 DEG C, and theoretical amount is precipitated as foundation using mercury in mercury antimony rich solution in electrolysis time, and cathode plate is stainless steel plate
Or titanium alloy sheet, anode are graphite plate or stainless steel plate；
Double electrodeposition condition are as follows: electrolytic solution ingredient are as follows: total mercury 3g/L, total antimony 40g/L, Na2S 160g/L, NaOH
25g/L；Current density 155A/m2, electrolyte circulation rate are as follows: 17L/ slot point, solution temperature are 55 DEG C；Electrolysis time
2.5h is electrolysed the reaction of generation are as follows:
Anode reaction formula are as follows: 4OH—-4e=H2O+O2,
Anode reaction formula are as follows: Sb3++3e=Sb,Hg2++2e=Hg；
Cathode-anode plate is identical as an electro-deposition；The mercury antimony alloy and mercury antimony lean solution that one double electrodeposition generates；Wherein, right
Mercury antimony lean solution, which is centrifuged, obtains vulcanized sodium crystallization, and mercury antimony lean solution crystallizes out vulcanized sodium using water cooling by the way of, mother liquor and
It leaches after primary alkali leachate, the mixing of secondary leaching filtrate, mercury antimony is extracted jointly again；
4) mercury antimony alloy thermal release；Thermal release is carried out to the mercury antimony alloy generated by a double electrodeposition, using vacuum
Smelting furnace purges furnace air using nitrogen before thermal release, is subsequently placed into mercury antimony alloy, into thermal release process, thermal release adds
Temperature uses 20 degree per minute, is heated to 520 DEG C of progress constant temperature, 2.8 h of constant temperature, and mercuryvapour condensation enters water absorption tower and becomes thick
Mercury, needle antimony enter coarse antimony refining process；
5) thick mercury purification, coarse antimony refining.Thick mercury carries out impurity removal and purification using the concentrated sulfuric acid or concentrated hydrochloric acid and produces smart mercury；Needle antimony is adopted
Refining No. 1 antimony of production is carried out with pyrogenic process.
This example mercury antimony comprehensive recovery is high, and mercury comprehensive recovery is greater than 99%, and antimony comprehensive recovery is greater than 98%.
Embodiment 3:
Used in the present embodiment mercury antimony composite ore collaboration extract mercury antimony method, used mercury antimony composite ore it is main
Ingredient are as follows: Hg0.52%, Sb1.53%, specifically includes the following steps:
1) 50 wood are crushed to after ore grinding to mercury antimony composite ore, carry out primary alkali leaching；Primary alkali leachate is
The mixed liquor of Na2S and NaOH, 180g/L containing Na2S, NaOH 50g/L；It is 5:1 that leachate, which consolidates mass ratio,；Extraction time
For 180min, extraction temperature is 35 DEG C, and stirring frequency is 140 revs/min；Guarantee that leaching rate of mercury is greater than 96%, antimony once leaches
Rate is greater than 93%；
2) primary to be separated by solid-liquid separation；Using full-automatic filters pressing mode, mercury antimony rich solution and a filter residue are isolated；Mercury antimony rich solution
Into electro-deposition process；One time filter residue enters secondary alkaline leaching；
Also carry out secondary alkaline leaching to a filter residue in the present embodiment: alkaline leaching liquid is the mixing of Na2S and NaOH
Liquid, 140g/L containing Na2S, NaOH 30g/L；It is 6:1 that secondary leachate, which consolidates mass ratio,；Extraction time is 120min, leaches temperature
Degree is 75 DEG C, and stirring frequency is 140 revs/min；Guarantee that the secondary leaching rate of mercury is greater than 98%, the secondary leaching rate of antimony is greater than 96%；
The present embodiment also carries out secondary separation of solid and liquid, secondary separation of solid and liquid to by the alkaline leaching liquid of secondary alkaline leaching
Technical process are as follows: use full-automatic filters pressing mode, isolate secondary filtrate and secondary filter residue；Secondary filtrate and primary leaching work
Primary alkali in sequence leaches jointly after leaching mixed liquor mixing, re-starts the extraction of mercury antimony；Secondary filter residue is carried out simultaneously
Washing, secondary residue washing process are as follows: secondary filter residue is washed through warm water, using repeatedly, washing times are 3 times on a small quantity；Cleaning solution
It is leached jointly after being mixed with secondary leaching mixed liquor；Washing residue is stored up or is comprehensively utilized after filters pressing is handled；
3) mercury antimony rich solution electro-deposition twice；The condition of mercury antimony rich solution electro-deposition are as follows: electrolytic solution ingredient are as follows: total mercury
100g/L, total antimony 95g/L, Na2S 140g/L, NaOH 30g/L；Current density 240A/m2, electrolyte circulation rate are as follows: 30L/
Slot point, solution temperature are 35 DEG C, and theoretical amount is precipitated as foundation using mercury in mercury antimony rich solution in electrolysis time, and cathode plate is stainless steel plate
Or titanium alloy sheet, anode are graphite plate or stainless steel plate；
Double electrodeposition condition are as follows: electrolytic solution ingredient are as follows: total mercury 4g/L, total antimony 50g/L, Na2S 180g/L, NaOH
30g/L；Current density 160A/m2, electrolyte circulation rate are as follows: 20L/ slot point, solution temperature are 60 DEG C；Electrolysis time 3h,
It is electrolysed the reaction occurred are as follows:
Anode reaction formula are as follows: 4OH—-4e=H2O+O2,
Anode reaction formula are as follows: Sb3++3e=Sb,Hg2++2e=Hg；
Cathode-anode plate is identical as an electro-deposition；The mercury antimony alloy and mercury antimony lean solution that one double electrodeposition generates；Wherein, right
Mercury antimony lean solution, which is centrifuged, obtains vulcanized sodium crystallization, and mercury antimony lean solution crystallizes out vulcanized sodium using water cooling by the way of, mother liquor and
It leaches after primary alkali leachate, the mixing of secondary leaching filtrate, mercury antimony is extracted jointly again；
4) mercury antimony alloy thermal release；Thermal release is carried out to the mercury antimony alloy generated by a double electrodeposition, using vacuum
Smelting furnace purges furnace air using nitrogen before thermal release, is subsequently placed into mercury antimony alloy, into thermal release process, thermal release adds
Temperature uses 20 degree per minute, is heated to 550 DEG C of progress constant temperature, 3 h of constant temperature, and mercuryvapour condensation enters water absorption tower and becomes thick mercury,
Needle antimony enters coarse antimony refining process；
5) thick mercury purification, coarse antimony refining.Thick mercury carries out impurity removal and purification using the concentrated sulfuric acid or concentrated hydrochloric acid and produces smart mercury；Needle antimony is adopted
Refining No. 1 antimony of production is carried out with pyrogenic process.
This example mercury antimony comprehensive recovery is high, and mercury comprehensive recovery is greater than 99%, and antimony comprehensive recovery is greater than 98%.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (6)
1. a kind of method that mercury antimony is extracted in the collaboration of mercury antimony composite ore, which comprises the steps of:
1) mercury antimony composite ore is crushed to particle diameter less than 80 mesh after ore grinding, and primary alkali leachate is then added and carries out
It is primary to leach；Wherein primary alkali leachate contains Na2S 160~180g/L, NaOH 30~50g/L；Primary alkali leachate with
The mass ratio of broken mercury antimony composite ore is 3 ~ 5:1；Extraction time is 120 ~ 180min, and temperature is 20 DEG C ~ 35 DEG C；It obtains
It obtains and once leaches material；
2) material filtering will be once leached, mercury antimony rich solution and a filter residue are obtained；Filtering uses full-automatic filters pressing mode；
3) mercury antimony rich solution carries out electro-deposition twice；When the electro-deposition of rich solution of mercury antimony, each constituent concentration of electrolytic solution are as follows: total mercury 85
~ 100g/L, total 80 ~ 95g/L of antimony, Na220 ~ 30g/L of S120 ~ 140g/L, NaOH；180 ~ 240A/m of current density2, electrolyte follows
Ring speed are as follows: 20 ~ 30L/ slot point, solution temperature are 20 DEG C ~ 35 DEG C, electrolysis time for 24 hours ~ 30h;
Cathode plate is stainless steel plate or titanium alloy sheet, and anode is graphite plate or stainless steel plate；
When mercury antimony rich solution double electrodeposition, each constituent concentration of electrolytic solution are as follows: total mercury 2 ~ 4g/L, total 30 ~ 50g/L of antimony, Na2S 140
20 ~ 30g/L of ~ 180g/L, NaOH；150 ~ 160A/m of current density2, electrolyte circulation rate are as follows: 15 ~ 20L/ slot point, solution
Temperature is 50 DEG C ~ 60 DEG C；Electrolysis time 2h ~ 3h；Cathode-anode plate is identical as an electro-deposition；Mercury is obtained after the completion of electro-deposition twice
Antimony alloy and mercury antimony lean solution；
4) mercury antimony alloy thermal release: using vacuum melting furnace, purges vacuum melting furnace air using nitrogen before thermal release, then
It is put into mercury antimony alloy, into the thermal release stage, heating uses 20 degree per minute, is heated to 500 ~ 550 DEG C of progress constant temperature, constant temperature
The h of 2.5h ~ 3, the steam condensation of generation enter water absorption tower and become thick mercury and needle antimony；
5) thick mercury purification, coarse antimony refining: thick mercury carries out impurity removal and purification using the concentrated sulfuric acid or concentrated hydrochloric acid and produces smart mercury；Needle antimony is using fire
Method carries out refining No. 1 antimony of production.
2. the method that mercury antimony is extracted in mercury antimony composite ore collaboration as described in claim 1, which is characterized in that mercury is primary in step 1)
Leaching rate is greater than 96%, and leaching rate of antimony is greater than 93%.
3. the method that mercury antimony is extracted in mercury antimony composite ore collaboration as described in claim 1, which is characterized in that one time filter residue is added two
Secondary alkaline leaching liquid carries out second and leaches, and secondary alkaline leaching liquid contains Na2S 120~140g/L, NaOH 20~30g/L；Two
The mass ratio of secondary alkaline leaching liquid and a filter residue is 4 ~ 6:1；Extraction time is 90 ~ 120min, and extraction temperature is 50 DEG C ~ 75
DEG C, obtain secondary leaching material.
4. the method that mercury antimony is extracted in mercury antimony composite ore collaboration as claimed in claim 3, which is characterized in that by secondary leaching material
Filtering, obtains secondary filtrate and secondary filter residue；Filtering uses full-automatic filters pressing mode；
Re-start the extraction of mercury antimony；
Secondary residue washing: secondary filter residue uses the injection mode in filter press frame through 30 DEG C ~ 40 DEG C water washings, washing, to
Washing rear liquid can stop containing NaOH lower than 3g/L, and the cleaning solution of acquisition returns to secondary alkaline leaching process；Residue is washed through filters pressing
It stores up or comprehensively utilizes after processing.
5. the method that mercury antimony is extracted in mercury antimony composite ore collaboration as claimed in claim 3, which is characterized in that secondary alkaline leaching
In technique, the secondary leaching rate of mercury is greater than 98%, and the secondary leaching rate of antimony is greater than 96%.
6. the method that mercury antimony is extracted in mercury antimony composite ore collaboration as described in claim 1, which is characterized in that warp in step 3)
Vulcanized sodium crystallization is carried out after the mercury antimony lean solution that electro-deposition twice obtains, mercury antimony lean solution crystallizes out vulcanized sodium by the way of water cooling,
After centrifuge separation, vulcanized sodium byproduct and mother liquor are obtained, mother liquor leaches mixed liquor with the primary alkali in step 1) and mixes,
Re-start the extraction of mercury antimony.
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| CN107973335A (en) * | 2017-11-24 | 2018-05-01 | 江苏盐城环保科技城重金属防治研究中心 | A kind of method of useless mercury catalyst alkaline wet recycling mercury |
| CN110106361A (en) * | 2019-06-13 | 2019-08-09 | 中国科学院过程工程研究所 | A kind of method that mercury tailing synchronous high-efficiency leaches mercury antimony |
| CN110106525B (en) * | 2019-06-18 | 2021-06-08 | 中国科学院过程工程研究所 | Method for extracting mercury and antimony through intensified electrolysis of low-concentration mercury and antimony solution |
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| WO2009129271A1 (en) * | 2008-04-14 | 2009-10-22 | Akridge James R | System for the sustainable recovery of metals from electronic waste |
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